JPH1046180A - Biodegradable strengthened vegetable oil grease - Google Patents

Abstract

PROBLEM TO BE SOLVED: To obtain a grease compsn. which is friendly to the environment and is produced from a vegetable oil-contg. antioxidant and a viscosity improver by compounding a specific base oil, a functional additive, and a thickener and to provide a method for preparing the same. SOLUTION: A lubricating grease friendly to the environment is obtd. by compounding a base oil which is a natural oil (e.g. sunflower or safflower oil) or synthetic triglyceride represented by formula I (wherein R<1> to R<3> are each a 7-23C aliph. group) formed from glycerine and at least one 8-22C linear fatty acid, at least one functional additive contg. an alkylphenol represented by formula II (wherein R<4> is 1-24C alkyl; and a is 1-5) and a benzotriazole compd. represented by formula III (wherein R<5> is H or a 1-24C alkyl) or an arom. amine represented by formula IV (wherein R<6> is a group represented by formula V; and R<7> and R<8> are each H or a 1-24C alkyl), a thickener which is a reaction product of a metal-base substance and a carboxylic acid or its ester, and if necessary a viscosity improver and a pour point depressant.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

[0001] The present invention relates to an environmentally friendly grease composition prepared from a vegetable oil-containing antioxidant and a viscosity improver, and to a method for preparing them. The antioxidants and metal passivators in this vegetable oil yield fortified vegetable oils. This grease composition is a grease containing no mineral oil. A thickener is prepared in situ within the fortified vegetable oil, wherein the thickener is a carboxylate of an alkali metal or alkaline earth metal.

[0002]

2. Description of the Related Art Grease manufacturers use fortified vegetable oils to
Attempts have been made to prepare alkali metal and alkaline earth metal greases with only some success. The high temperatures required for preparation degrade this vegetable oil thickener substitute and vegetable oil diluent. In addition, the high temperatures cause the antioxidants and viscosity modifiers to separate.

No. 2,697,693 (Browning et al., 1954)
December 21) relates to improvements in the production of lithium soap grease. More specifically, it comprises lithium 12-hydroxystearate or hydrogenated castor oil soap and a lubricant base (e.g., mineral lubricating oil, etc.)
The present invention relates to improvements in the production of greases containing.

No. 2,824,066 (Musselman et al., 195
February 18, 8) relates to multipurpose soda-based lubricating grease. The preparation of the grease preferably involves forming the fatty acid soap in mineral oil in situ. A typical preparation involves weighing a solvent-extracted oil and a calculated amount of sodium hydroxide into a mixing vessel, then heating these materials to an elevated temperature, typically above 150 ° F., and then Weighing the fatty acids into the mixer. Start the mixer again and continue heating at a temperature of approximately 300 ° F. After heating at high temperature for about 10-15 minutes,
Add additional solvent-extracted oil to the mixer until saponification is complete and continue heating until the total processing time of about 2-1 / 2 hours to 3 hours has elapsed. Then, stop heating,
During cooling of the crude grease mixture, an additional calculated amount of solvent extracted oil was added and the final oil addition was allowed to reach 225-230 ° F.
Perform at near temperature. Cooling is then continued until the grease is at a temperature suitable for packaging.

No. 4,303,538 (Pratt et al., 1981 Jan.
(February 1) relates to oxyaluminum acrylates containing greater than about 75 mol% aromatic carboxylic acids but less than about 95 mol% of adjustable aromatic acids; Aluminum can be used to produce apparently superior quality aluminum complex grease. Greases made from such oxyaluminum acrylates are produced without the use of water and do not produce water or alcohol as a by-product.

No. 4,392,967 (Alexander, 1983)
July 12, 2008) relates to a method for continuously producing lubricating grease using a screw process unit. More specifically, the method of this reference includes: (a) introducing feed and lubricating oil to selected locations of a screw process unit, wherein the unit performs different operating steps Containing a series of adjacent longitudinally connected barrel sections for accommodating a rotary screw device that traverses the interior of the barrel section and performs the desired operation. Having a dividing element along its length; (b) mixing and transporting the feed material along the process unit passing through the adjacent barrel portion by continuous operation of the rotating screw (C) transporting the substance through the process unit by controlling the temperature of the substance and using various heat exchange means, wherein the heat exchange means is in or adjacent to each barrel. Is located, At (d) selected barrel discharging point of the process unit; dispersion, reaction, dehydration and / or promoting perform operational steps of homogenization, step
Draining the water obtained by dehydrating the feed mixture; (e) following the dehydration step, introducing additional oil and / or additives downstream of the barrel section; (f) the screw Homogenizing the complete grease formulation by continuously rotating the apparatus; and (g) removing the finished lubricating grease from the terminal barrel portion of the screw process unit.

US Pat. No. 5,116,522 (Brown et al., May 26, 1992) relates to lubricating compositions with improved low and high temperature properties. More specifically, (1) lubricating oil, (2) thickener, (3) VI improver, and (4) ethylene and at least one selected from the group of vinyl acetate, alkyl acrylates and alkyl methacrylates. Lubricating compositions containing copolymers with the compounds have been found to have both good hot tack and cold slump performance. The ethylene copolymer used in the present invention has at least about 40 g / 10
Must have a melt index of about 10 ~
It should contain about 40% by weight of vinyl acetate, alkyl acrylate or alkyl methacrylate. Preferably, the melt index is between about 40 g / 10 minutes and about 10,000
0 g / 10 min, more preferably about 40 g / 10 min and about 5.0
Between 00 g / 10 min, most preferably about 40 g / 10 min and about 2,50
Should be between 0 g / 10 min.

US Pat. No. 5,154,840 (Drake et al., January 1992)
(October 13) provides an environmentally friendly grease composition.
The base component of the lubricating composition comprises, based on the total weight of the composition, a white mineral oil in an amount of about 65 to about 85% by weight, an extreme pressure containing a solid viscosity improver in an amount of about 1 to about 20% by weight. Additive,
And one or more dispersible additives in small amounts sufficient to enhance the performance of the grease. Each of the extreme pressure additives, thickeners, and one or more oil dispersible additives comprises a heavy metal (especially arsenic, antimony, barium, cadmium, chromium, copper, iron,
(Lead, mercury, molybdenum, nickel, selenium, vanadium and zinc).

No. 5,256,321 (Todd, Oct. 1993)
26) relates to an improved grease composition substantially free of boron and boron-containing compounds, the composition comprising a major amount of an oil-based simple metal soap thickened base grease,
And in small quantities the drop point of this base grease (ASTM procedur
e measured by D-2265) in an amount sufficient to raise at least 30 ° C. at least one phosphorus and sulfur containing composition.

[0010]

SUMMARY OF THE INVENTION An object of the present invention is to provide an environmentally friendly grease composition prepared from a vegetable oil-containing antioxidant and a viscosity improver, and a method for preparing the same.

[0011]

The present invention provides the following (A):
Provide an environmentally friendly lubricating grease containing (B) and (C): (A) a base oil, wherein the base oil is a natural oil or a synthetic triglyceride of the formula:

[0012]

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Here, R ¹ , R ² and R ³ are from about 7 to about 23
(B) at least one of the following (1), (2) or (3):
Kinds of performance additives: (1) Alkylphenol of the following formula:

[0014]

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Wherein R ⁴ is an alkyl group containing from 1 to about 24 carbon atoms, and a is an integer from 1 to 5; (2) benzotriazole of the formula:

[0016]

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Here, R ⁵ is hydrogen or one to about 24
Or an alkyl group having three carbon atoms; or (3) an aromatic amine of the formula:

[0018]

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Here, R ⁶ is

[0020]

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And R ⁷ and R ⁸ are independently:
Hydrogen or an alkyl group containing from 1 to about 24 carbon atoms; and (C) a thickener, wherein the thickener (C) comprises (C1) a metal-based material. And (C2) a reaction product of a carboxylic acid or an ester thereof, wherein the metal-based material (C1) is
A metal oxide, metal hydroxide, metal carbonate or metal bicarbonate, wherein the metal is an alkali metal or alkaline earth metal, wherein the carboxylic acid or ester thereof (C2) Has the formula R ¹⁸ (COOR ¹⁹ ) _n , wherein R ¹⁸ is an aliphatic group containing from 4 to about 29 carbon atoms, and R ¹⁹ is hydrogen or 1 to 4 And n is an integer from 1 to 4, where the equivalent ratio of (C1) :( C2) is 1: 0.70 to 1.
It is 10.

In one embodiment, the alkyl phenol has the formula:

[0023]

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Here, R ⁴ is t-butyl.

In another embodiment, R ⁵ in (B) (2) is
It is a methyl group.

In still another embodiment, in (B) (3)
R ⁶ is

[0027]

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And R ^{7 and} R ⁸ are nonyl groups.

In yet another embodiment, the alkali metal of (C1) includes lithium, sodium or potassium, and the alkaline earth metal of (C1) includes magnesium, calcium or barium.

In yet another embodiment, (C1) is lithium hydroxide or calcium hydroxide.

In yet another embodiment, R ¹⁹ is hydrogen and the carboxylic acid is 6-hydroxystearic acid, 12-hydroxystearic acid, 14-hydroxystearic acid, 16-hydroxystearic acid or ricinoleic acid Or a dihydroxymonocarboxylic acid including 9,10-dihydroxystearic acid.

In yet another embodiment, the natural oil is
Sunflower oil, safflower oil, corn oil, soybean oil,
Rapeseed oil, coconut oil, lesquerella oil, castor oil, canola oil or peanut oil.

In yet another embodiment, the synthetic triglyceride is an ester of at least one straight chain fatty acid and glycerol, wherein the fatty acid contains from 8 to 22 carbon atoms.

In yet another embodiment, the natural oil is
A genetically modified vegetable oil, wherein R ¹ , R ² and R ³ are aliphatic groups having at least 60% monounsaturated properties, said monounsaturated properties resulting from oleic acid residues, The ratio of the oleic acid portion to the linoleic acid portion is from 2 to 90 and the genetically modified vegetable oil is a genetically modified sunflower oil, a genetically modified corn oil, a genetically modified soybean oil Genetically modified rapeseed oil, genetically modified canola oil, genetically modified safflower oil or genetically modified peanut oil.

In still another embodiment, the lubricating grease further comprises the following (D) or (E): (D) a hydrogenated block copolymer comprising a normal block copolymer or a random block copolymer. A viscosity improver containing a coalesce, wherein the normal block copolymer is made from a vinyl-substituted aromatic compound and an aliphatic conjugated diene, and the normal block copolymer is at least one of the vinyl-substituted aromatic compounds. And from 2 to about 5 polymer blocks having at least one polymer block and at least one polymer block of the aliphatic conjugated diene, wherein the random block copolymer comprises a vinyl-substituted aromatic monomer and Manufactured from an aliphatic conjugated diene monomer, the total amount of the vinyl-substituted aromatic block in the block copolymer is about
The total amount of the diene blocks in the block copolymer ranges from about 30% to about 80% by weight, and the normal block copolymer and the random The number average molecular weight of the block copolymer is about 5,000
A viscosity modifier ranging from 0 to about 1,000,000; or (E) a pour point depressant, or a mixture thereof.

In still another embodiment, the normal block copolymer has two or three polymer blocks in total, and the number average molecular weight of the normal block copolymer and the random block copolymer. Is about 30,000 to about
200,000, and in the block copolymer, the total amount of the conjugated diene is about 40% to about 60% by weight;
The total amount of the vinyl-substituted aromatic compound is about 40% by weight to about 40% by weight.
60% by weight, the conjugated diene is isoprene or butadiene, the vinyl-substituted aromatic compound is styrene, and the hydrogenated normal block copolymer and the random block copolymer have a residual content of 0.5% or less. Contains olefinic unsaturation.

In yet another embodiment, the pour point depressant (E) is a mixed ester characterized by the low temperature improving properties of the ester of the carboxy-containing interpolymer, wherein the interpolymer comprises from about 0.05 to about 2 It has a reduced specific viscosity and is derived from at least two monomers, one of which is a low molecular weight aliphatic olefin, styrene or substituted styrene, wherein the substituent is from one to about 18 A hydrocarbyl group containing up to carbon atoms, and the other of the monomers is α,
a β-unsaturated aliphatic acid, anhydride or ester thereof, wherein the mixed ester has substantially no titratable acidity and is derived from the carboxy group of the mixed ester;
The following pendant polar groups (a), (b) and (c) are characterized by being present in the polymer structure: (a) at least 8 aliphatic carbon atoms in the ester group Having a relatively high molecular weight carboxylate group, optionally (b) having no more than 7 aliphatic carbon atoms in the ester group, a relatively low molecular weight carboxylate group, Wherein when (b) is present, the pour point depressant has a (a) :( b) molar ratio of (1-20): 1, a relatively low molecular weight carboxylic ester group, and Optionally, (c) a carbonyl-amino group derived from an amino compound having one primary or secondary amino group, wherein (b) and (c) are present At this time, the molar ratio of (a) :( b) :( c) of the pour point depressant is (50-100):
(5-50): a carbonyl-amino group which is (0.1-15).

In yet another embodiment, the molar ratio of (a) :( b) of the pour point depressant is (1-10): 1, or (a): The molar ratio of (b) :( c) is (70 to
85): (15-30): (1-5).

In yet another embodiment, the interpolymer is a styrene-maleic anhydride interpolymer having a reduced specific viscosity of about 0.1 to about 1, wherein the relatively high molecular weight carboxylic ester group (a) is Having from 8 to 24 aliphatic carbon atoms, the relatively low molecular weight carboxylic acid ester group (b) has from 3 to 5 carbon atoms, and the carbonyl-amino group (c ) Is derived from a primary aminoalkyl-substituted tertiary amine.

In yet another embodiment, the carboxy-containing interpolymer is a terpolymer of 1 mole of styrene, 1 mole of maleic anhydride, and less than about 0.3 mole of vinyl monomer.

In yet another embodiment, the pour point depressant (E) is an acrylate polymer of the formula:

[0042]

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Wherein R ⁹ is hydrogen or a lower alkyl group containing 1 to about 4 carbon atoms, R ¹⁰ is an alkyl group containing about 1 to about 24 carbon atoms, cyclo A mixture of alkyl or aromatic groups, and x is an integer that provides the acrylate polymer with a weight average molecular weight (Mw) of about 5,000 to about 1,000,000.

In yet another embodiment, the pour point depressant (E) is a mixture of compounds having the following general structure:

[0045]

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Here, Ar, Ar ′ and Ar ″ independently represent
An aromatic moiety containing from 1 to 3 aromatic rings, wherein the mixture is free of substituents or has one substituent, two substituents and three substituents. R ¹¹ and R ¹² are independently alkylene containing from about 1 to 100 carbon atoms, n is from 0 to 1
000, and n 'is 0 or 1 and X is 1
A hydrocarbylene group containing from 1 to 24 carbon atoms, wherein the compound has a molecular weight in the range of about 300 to about 300,000.

In still another embodiment, the pour point depressant (E) is obtained by mixing an acrylate monomer of the following formula and a nitrogen-containing monomer with the nitrogen-containing monomer in an amount of 0.001 to 0.1 mole of the acrylate monomer. A nitrogen-containing polymer prepared by polymerizing at a rate of ~ 1.0 mol,
The nitrogen-containing monomer is 4-vinylpyridine, 2-vinylpyridine, 2-N-morpholinoethyl methacrylate, N, N-dimethylaminoethyl methacrylate and N, N-methacrylate.
Selected from the group consisting of dimethylaminopropyl:

[0048]

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Here, R ¹³ is hydrogen, or 1 to about 8
An alkyl group containing 6 carbon atoms and R ¹⁴
Is an alkyl, cycloalkyl or aromatic group containing from 1 to about 30 carbon atoms.

In yet another embodiment, the pour point depressant (E) is a terpolymer, and the terpolymer is a terpolymer.
At a temperature of 25 ° C. to 150 ° C., having a specific viscosity of 0.090 to 0.800 per 100 ml of benzene at a temperature of 25 ° C. to 150 ° C. Is prepared by polymerizing a mixture of 0.5 to 1 mol of a mixture of the following (b) and (c): (a) a fumaric acid ester of the formula:

[0051]

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Wherein R ¹⁵ is an alkyl group containing 10 to 18 carbon atoms; (b) a vinyl ester of the following formula:

[0053]

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Wherein R ¹⁶ is an alkyl group containing 2 to 10 carbon atoms; (c) a vinyl ether of the following formula:

[0055]

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Here, R ¹⁷ is an alkyl group containing 1 to 10 carbon atoms, and the molar ratio of (b) to (c) in the mixture is 9: 1 to 1: 9. Range.

The present invention also provides a method for preparing an environmentally friendly grease, comprising the steps of: (a) preparing a solution of the following (A) and (B): (A) a base oil Wherein the base oil is a natural oil or a synthetic triglyceride of the formula:

[0058]

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Here, R ¹ , R ² and R ³ are from about 7 to about 23
(B) at least one of the following (1), (2) or (3):
Kinds of performance additives: (1) Alkylphenol of the following formula:

[0060]

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Wherein R ⁴ is an alkyl group containing from 1 to about 24 carbon atoms, and a is an integer from 1 to 5; (2) benzotriazole of the formula:

[0062]

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Here, R ⁵ is hydrogen or one to about 24
Or an alkyl group having three carbon atoms; or (3) an aromatic amine of the formula:

[0064]

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Here, R ⁶ is

[0066]

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And R ⁷ and R ⁸ are independently:
Hydrogen or an alkyl group containing from 1 to about 24 carbon atoms; or preparing a solution of the following (A), (B) and (D): (A) a base oil; A) a performance additive; and (D) a viscosity improver, wherein the viscosity improver is a hydrogenated block copolymer including a normal block copolymer or a random block copolymer, The copolymer is made from a vinyl-substituted aromatic compound and an aliphatic conjugated diene, and the normal block copolymer comprises at least one polymer block of the vinyl-substituted aromatic compound and at least one of the aliphatic conjugated diene.
Having from 2 to about 5 polymer blocks, wherein the random block copolymer is made from a vinyl-substituted aromatic monomer and an aliphatic conjugated diene monomer; The total amount of the vinyl substituted aromatic blocks in the block copolymer ranges from about 20% to about 70% by weight, and the total amount of the diene blocks in the block copolymer ranges from about 30% to about 80% by weight. The number average molecular weight of the normal block copolymer and the random block copolymer ranges from about 5,000 to about 1,000,000;
Or a process for producing a solution of the following (A), (B) and (E): (A) a base oil; (B) a performance additive; and (E) a pour point depressant, said pour point depressant. Agent (E) comprises a mixed ester characterized by the low temperature improving properties of the ester of the carboxy-containing interpolymer, the interpolymer having a reduced specific viscosity of about 0.05 to about 2 and at least two monomers Wherein one of the monomers is a low molecular weight aliphatic olefin, styrene or substituted styrene, wherein the substituent is a hydrocarbyl group containing from 1 to about 18 carbon atoms; And the other of the monomers is an α, β-unsaturated aliphatic acid, anhydride or ester thereof, the mixed ester has substantially no titratable acidity, and the carboxy group of the mixed ester The following (a), (b) And (c) the pendant polar group is characterized by being present in the polymer structure: (a) a relatively high molecular weight carboxylic acid having at least 8 aliphatic carbon atoms in the ester group; An acid ester group, optionally (b) a relatively low molecular weight carboxylic ester group having 7 or less aliphatic carbon atoms in the ester group, wherein (b) is present At this time, the molar ratio of (a) :( b) of the pour point depressant is (1-20): 1, a relatively low molecular weight carboxylic acid ester group, and if necessary, (c) 1 A carbonyl-amino group derived from an amino compound having one primary amino group or a secondary amino group, wherein (b) and (c) are present when the pour point depressant ( The molar ratio of a) :( b) :( c) is (50-100):
(5-50): a carbonyl-amino group which is (0.1-15);
Alternatively, the pour point depressant contains an acrylate polymer of the formula:

[0068]

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Here, R ⁹ is hydrogen or a lower alkyl group containing 1 to about 4 carbon atoms, R ¹⁰ is an alkyl group containing about 1 to about 24 carbon atoms, cycloalkyl A mixture of alkyl or aromatic groups, and x is an integer that provides the acrylate polymer with a weight average molecular weight (Mw) of about 5,000 to about 1,000,000; or the pour point depressant comprises: Contains a mixture of compounds having the general structural formula:

[0070]

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Here, Ar, Ar ′ and Ar ″ are independently
An aromatic moiety containing from 1 to 3 aromatic rings, wherein the mixture is free of substituents or has one substituent, two substituents and three substituents. R ¹¹ and R ¹² are independently alkylene containing from about 1 to 100 carbon atoms, n is from 0 to 1
000, and n 'is 0 or 1 and X is 1
Or a pour point depressant, wherein the pour point depressant comprises an acrylate monomer of the formula: and a nitrogen-containing monomer, for each mole of the acrylate monomer And a nitrogen-containing polymer prepared by polymerizing the nitrogen-containing monomer in a ratio of 0.001 to 1.0 mol:

[0072]

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Here, R ¹³ is hydrogen, or 1 to about 8
An alkyl group containing 6 carbon atoms and R ¹⁴
Is an alkyl, cycloalkyl, or aromatic group containing from 1 to about 30 carbon atoms; or the pour point depressant is a terpolymer, and the terpolymer is , 30
C., having a specific viscosity of 0.090 to 0.800 measured in a solution of 5 grams of the terpolymer per 100 milliliters of benzene, and at a temperature of 25 ° C. to 150 ° C., 1 mol of the following (a): It is prepared by polymerizing 0.5 to 1 mol of a mixture of the following (b) and (c): (a) fumaric ester of the formula:

[0074]

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Wherein R ¹⁵ is an alkyl group containing 10 to 18 carbon atoms; (b) a vinyl ester of the following formula:

[0076]

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Wherein R ¹⁶ is an alkyl group containing 2 to 10 carbon atoms; (c) a vinyl ether of the following formula:

[0078]

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Here, R ¹⁷ is an alkyl group containing 1 to 10 carbon atoms, and the molar ratio of (b) to (c) in the mixture is 9: 1 to 1: 9. Range; or
Steps of preparing solutions of (A), (B), (D) and (E): (A) a base oil; (B) a performance additive; (D) a viscosity improver; and (E) a pour point depressant. And (C1) a metal-based material and (C1)
2) adding a carboxylic acid or an ester thereof, thereby providing a mixture: wherein the metal-based material
(C1) comprises a metal oxide, metal hydroxide, metal carbonate or metal bicarbonate, wherein the metal is an alkali metal or alkaline earth metal, wherein the carboxylic acid or The ester (C2) has the formula R ¹⁸ (COOR ¹⁹ ) _n , where R ¹⁸ is an aliphatic group containing 4 to about 29 carbon atoms, and R ¹⁹ is hydrogen, Or an aliphatic group containing 1 to 4 carbon atoms, and n is 1 to
4, where the equivalent ratio of (C1) :( C2) is 1:
0.70 to 1.10, wherein the base oil (A), the metal base material (C1) and the carboxylic acid or its ester (C2)
Weight ratio to the sum of is 50:50 to 95: 5; and (b) heating the mixture to a temperature of about 82 ° C to about 105 ° C;
(C) forming a thickening agent; (c) heating the mixture to about 145 ° C. in the case of an alkaline earth metal.
Final temperature, or about 200 ° C for alkali metals
And (d) cooling the mixture to form a grease, wherein the performance additive (B) is present at 0.5-10% by weight and the viscosity The modifier (D) is present at 0.5-7.5% by weight and the pour point depressant (E) is present at 0.5-7.5% by weight.

The present invention also provides a method for preparing an environmentally friendly grease, comprising the steps of: (a) preparing a solution of the following (A) and (B): (A) a base oil Wherein the base oil is a natural oil or a synthetic triglyceride of the formula:

[0081]

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Here, R ¹ , R ² and R ³ are from about 7 to about 23
(B) at least one of the following (1), (2) or (3):
Kinds of performance additives: (1) Alkylphenol of the following formula:

[0083]

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Wherein R ⁴ is an alkyl group containing from 1 to about 24 carbon atoms, and a is an integer from 1 to 5; (2) a benzotriazole of the formula:

[0085]

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Here, R ⁵ is hydrogen or one to about 24
Or an alkyl group having three carbon atoms; or (3) an aromatic amine of the formula:

[0087]

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Here, R ⁶ is

[0089]

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And R ⁷ and R ⁸ are independently:
Hydrogen or an alkyl group containing from 1 to about 24 carbon atoms; or preparing a solution of the following (A), (B) and (D): (A) a base oil; (D) a viscosity improver, wherein the viscosity improver is a hydrogenated block copolymer including a normal block copolymer or a random block copolymer, and the normal block copolymer Is prepared from a vinyl-substituted aromatic compound and an aliphatic conjugated diene, and the normal block copolymer comprises at least one polymer block of the vinyl-substituted aromatic compound and at least one polymer of the aliphatic conjugated diene. A random block copolymer having two to about five polymer blocks having united blocks, wherein the random block copolymer is made from a vinyl-substituted aromatic monomer and an aliphatic conjugated diene monomer; The total amount of the vinyl substituted aromatic blocks in the range of about 20 wt% to about 70 wt%, the total amount of said diene block of the block copolymer is about 30
% To about 80% by weight, and the number average molecular weight of the normal block copolymer and the random block copolymer ranges from about 5,000 to about 1,000,000; or the following (A), (B) ) And (E): (A) a base oil; (B) a performance additive; and (E) a pour point depressant, wherein the pour point depressant (E) comprises A mixed ester characterized by the low temperature improving properties of the ester of the polymer, wherein the interpolymer has a reduced specific viscosity of about 0.05 to about 2 and is derived from at least two monomers, one of the monomers being A low molecular weight aliphatic olefin, styrene or substituted styrene, wherein the substituent is a hydrocarbyl group containing from 1 to about 18 carbon atoms and the other of the monomers is α, β-unsaturated aliphatic acids, An anhydride or an ester, wherein the mixed ester has substantially no titratable acidity and is derived from the carboxy group of the mixed ester and comprises the following (a), (b) and (c): A pendant polar group is characterized by the presence in the polymer structure: (a) a relatively high molecular weight carboxylic ester group having at least 8 aliphatic carbon atoms in the ester group; (B) a relatively low molecular weight carboxylic ester group having 7 or less aliphatic carbon atoms in the ester group, wherein (b) is present when the pour point The molar ratio of (a) :( b) of the depressant is (1-20): 1, relatively low molecular weight carboxylic acid ester groups, and optionally (c) one primary A carbonyl-amino group derived from an amino compound having an amino group or a secondary amino group; Wherein the molar ratio of (b) and when (c) is present, the flow moving point depressant (a) :( b) :( c), (50~100):
(5-50): a carbonyl-amino group which is (0.1-15);
Alternatively, the pour point depressant contains an acrylate polymer of the formula:

[0091]

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Here, R ⁹ is hydrogen or a lower alkyl group containing 1 to about 4 carbon atoms, R ¹⁰ is an alkyl group containing about 1 to about 24 carbon atoms, cycloalkyl A mixture of alkyl or aromatic groups, and x is an integer that provides the acrylate polymer with a weight average molecular weight (Mw) of about 5,000 to about 1,000,000; or the pour point depressant comprises: Contains a mixture of compounds having the general structural formula:

[0093]

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Here, Ar, Ar ′ and Ar ″ independently represent
An aromatic moiety containing from 1 to 3 aromatic rings, wherein the mixture is free of substituents or has one substituent, two substituents and three substituents. R ¹¹ and R ¹² are independently alkylene containing from about 1 to 100 carbon atoms, n is from 0 to 1
000, and n 'is 0 or 1 and X is 1
Or a pour point depressant, wherein the pour point depressant comprises an acrylate monomer of the formula: and a nitrogen-containing monomer, for each mole of the acrylate monomer And a nitrogen-containing polymer prepared by polymerizing the nitrogen-containing monomer in a ratio of 0.001 to 1.0 mol:

[0095]

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Here, R ¹³ is hydrogen or 1 to about 8
An alkyl group containing 6 carbon atoms and R ¹⁴
Is an alkyl, cycloalkyl, or aromatic group containing from 1 to about 30 carbon atoms; or the pour point depressant is a terpolymer, and the terpolymer is , 30
C., having a specific viscosity of 0.090 to 0.800 measured in a solution of 5 grams of the terpolymer per 100 milliliters of benzene, and at a temperature of 25 ° C. to 150 ° C., 1 mol of the following (a): It is prepared by polymerizing 0.5 to 1 mol of a mixture of the following (b) and (c): (a) fumaric ester of the formula:

[0097]

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Wherein R ¹⁵ is an alkyl group containing 10 to 18 carbon atoms; (b) a vinyl ester of the following formula:

[0099]

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Wherein R ¹⁶ is an alkyl group containing 2 to 10 carbon atoms; (c) a vinyl ether of the following formula:

[0101]

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Here, R ¹⁷ is an alkyl group containing 1 to 10 carbon atoms, and the molar ratio of (b) to (c) in the mixture is 9: 1 to 1: 9. Range; or
Steps of preparing solutions of (A), (B), (D) and (E): (A) a base oil; (B) a performance additive; (D) a viscosity improver; and (E) a pour point depressant. And (C1) a metal-based material and (C1)
2) adding a carboxylic acid or an ester thereof, thereby providing a first mixture: wherein the metal-based material (C1) is a metal oxide, a metal hydroxide, a metal carbonate or a metal oxide; A carbonate, wherein the metal is an alkali metal or alkaline earth metal, wherein the carboxylic acid or its ester (C2) has the formula R ¹⁸ (COOR ¹⁹ ) _n , Wherein R ¹⁸ is an aliphatic group containing from 4 to about 29 carbon atoms, R ¹⁹ is hydrogen, or an aliphatic group containing from 1 to 4 carbon atoms, and n Is 1
Where the equivalent ratio of (C1) :( C2) is
1: 0.70 to 1.10, wherein the base oil (A), the metal base material (C1) and the carboxylic acid or its ester
The weight ratio of (C2) to the sum is from 50:50 to 90:10; and (b) heating the first mixture to a temperature of about 82 ° C to about 105 ° C, Forming an agent, thereby forming a heated first mixture; (c) subjecting the heated first mixture to a final temperature of about 145 ° C. in the case of an alkaline earth metal, or in the case of an alkali metal Heating to a final temperature of about 200 ° C .; (d) at 110-145 ° C. for alkaline earth metals, or 170-200 ° C. for alkali metals,
The next part of (A), or ( Adding a solution of A) and (B), or a solution of (A), (B), (D) and / or (E) to provide a second mixture; and (e) the second mixture Cooling to form a grease: wherein the performance additive (B) is present at 0.5-10% by weight, the viscosity modifier (D) is present at 0.5-7.5% by weight, And the pour point depressant (E) is present at 0.5-7.5% by weight.

[0103]

DETAILED DESCRIPTION OF THE INVENTION (A) Base Oil In practicing the present invention, the base oil is a synthetic triglyceride or natural oil of the formula:

[0104]

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Here, R ¹ , R ² and R ³ are from about 7 to about 23
Is an aliphatic hydrocarbyl group containing two carbon atoms. As used herein, the term "hydrocarbyl group" refers to a group having a carbon atom directly attached to the remainder of the molecule. These aliphatic hydrocarbyl groups include: (1) an aliphatic hydrocarbon group; ie, an alkyl group (eg,
Heptyl, nonyl, undecyl, tridecyl, heptadecyl); alkenyl groups containing a single double bond (eg, heptenyl, nonenyl, undecenyl, tridecenyl, heptadecenyl, heneicosanyl); containing two or three double bonds Alkenyl groups (e.g., 8,11-
Heptadecadienyl and 8,11,14-heptadecatrienyl). All these isomers are included, but linear groups are preferred.

(2) Substituted aliphatic hydrocarbon groups; that is, groups containing non-hydrocarbon substituents which, within the context of the present invention, do not primarily alter the hydrocarbon nature of the group. One skilled in the art will know suitable substituents; examples include hydroxy,
Carboalkoxy (especially lower carboalkoxy) and alkoxy (especially lower alkoxy) include "lower"
The term refers to groups containing up to 7 carbon atoms.

(3) hetero groups; that is, within the context of the present invention, while having predominantly aliphatic hydrocarbon character,
Having atoms other than carbon present in the ring or chain,
Others are groups composed of aliphatic carbon atoms. Suitable heteroatoms will be apparent to those skilled in the art and include, for example, oxygen, nitrogen and sulfur.

Naturally occurring triglycerides include vegetable oil triglycerides. Some synthetic triglycerides are formed by the reaction of 1 mole of glycerol with 3 moles of a fatty acid or mixture of fatty acids. In preparing synthetic triglycerides, the fatty acids contain from 8 to 24 carbon atoms. Preferably, the fatty acid is oleic, linoleic, linolenic or a mixture thereof. Most preferably, the fatty acid is oleic acid. Of these vegetable oil triglycerides and synthetic triglycerides, vegetable oil triglycerides are preferred. Preferred vegetable oils include soybean oil, rapeseed oil, sunflower oil, coconut oil, lesquerella oil, canola oil,
In a preferred embodiment, where there are peanut oil, safflower oil and castor oil, the aliphatic hydrocarbyl group is such that the triglyceride is at least 60% monounsaturated, preferably at least 70% monounsaturated, most preferably Is made to have at least 80% monounsaturation. Examples of naturally occurring triglycerides useful in the present invention are vegetable oils that have been genetically modified so that they have a higher than normal oleic acid content. Normal sunflower oil has an oleic acid content of 25-30%. Genetically modifying this sunflower seed results in sunflower oil having an oleic acid content of about 60% to about 92%. That is, the R ¹ group, R ² and R ³ groups are heptadecenyl, 1,2,3 propanetriol yl group, i.e. -CH ₂ CHCH ₂ - bonded to R ¹ COO ^-, R ² COO ^- and R ³ COO
^- is the residue of oleic acid molecule. US Patent 4,627,1
Nos. 92 and 4,743,402 are incorporated herein by reference for their disclosure of the preparation of high oleic sunflower oil.

For example, a triglyceride composed solely of the oleic acid moiety has an oleic acid content of 100% and therefore a monounsaturation content of 100%. When the triglyceride is composed of the acid portion of 70% oleic acid, 10% stearic acid, 13% palmitic acid and 7% linoleic acid, its monounsaturation content is 70%. A preferred triglyceride oil is a high oleic triglyceride oil, ie, a genetically modified vegetable oil (at least 60%) triglyceride oil. Typical high oleic vegetable oils used in the present invention are high oleic safflower oil, high oleic canola oil, high oleic peanut oil, high oleic corn oil, high oleic rapeseed oil, high oleic sunflower oil. And high oleic soybean oil. Canola oil is a variant of rapeseed oil containing less than 1% erucic acid. A preferred high oleic vegetable oil is high oleic sunflower oil obtained from Helianthus sp. This product is
Available from SVO Enterprises (Eastlake, Ohio) as Sunyl® high oleic sunflower oil. Sunyl
80 is high oleic triglyceride, where:
The acid portion is composed of 80% oleic acid. Other preferred high oleic vegetable oils include Brassica campestri
There is high oleic rapeseed oil obtained from s or Brassica napus, which is also available from SVO Enterprises as RS high oleic rapeseed oil. RS80 oil refers to rapeseed oil whose acid portion is composed of 80% oleic acid.

It is further noted that genetically modified vegetable oils have a high oleic acid content with reduced di- and triunsaturated acids. Normal sunflower oil is 20-40
% Oleic acid and 50-70% linoleic acid. This gives a content of mono- or di-unsaturated acid moieties of 90% (ie (20 + 70)% or (40 + 50)%). Genetically modified vegetable oils result in vegetable oils having lower di- or tri-unsaturation. The genetically modified oils of the present invention have a ratio of about 2 to about 90 oleic acid moieties to linoleic acid moieties. Triglyceride oil
A content of 60% oleic acid and 30% linoleic acid gives a ratio of 2. A triglyceride oil composed of 80% oleic acid and 10% linoleic acid yields a ratio of 8. For a triglyceride oil composed of 90% oleic acid and 1% linoleic acid, a ratio of 90 is obtained. This ratio for normal sunflower oil is 0.5 (30% oleic acid and 60% linoleic acid).

In another embodiment, the genetically modified vegetable oil can be sulfurized. The sulfidation of compounds containing double bonds, although previously known in the art,
Sulfidation of the genetically modified vegetable oil must be done in a manner that does not result in total vulcanization. The direct sulfidation performed by reacting the genetically modified vegetable oil with sulfur results in a vulcanized product, which, if not solid, has a very high viscosity.
This is not a suitable base oil (A) for grease preparation. Other sulfurization methods are well known in the art. A small number of these sulfurization methods are sulfur monochloride; sulfur dichloride;
Sodium sulfide / H ₂ S / sulfur; sodium sulfide / H ₂ S; sodium sulfide / sodium mercaptide / sulfur or sulfuration using a chain transfer agent. A particularly preferred genetically modified sulfurized vegetable oil is sulfurized Sunyl 80® oil available from Hornet Brothers.

The genetically modified sulfurized vegetable oil generally has a sulfur level of 5 to 15% by weight, preferably 7 to 13% by weight, most preferably 8.5 to 11.5% by weight.

The use of this genetically modified sulfurized vegetable oil as component (A) is one method of preparing greases with even higher antiwear or load bearing performance.

Component (A) can be all genetically modified vegetable oil, all genetically modified sulfurized vegetable oil, or a mixture of genetically modified vegetable oil and genetically modified sulfurized vegetable oil. When using a mixture, the ratio of genetically modified vegetable oil to genetically modified sulfurized vegetable oil is 8
5:15 to 15:85.

(B) Performance additive The base oil (A) is fortified with the performance additive (B). Performance enhanced by these additives includes abrasion resistance, antioxidant properties,
There are areas such as rust / corrosion prevention, metal passivation, extreme pressure properties, friction adjustment.

This performance additive (B) is selected from the group consisting of: (1) alkylphenols, (2) benzotriazoles, and (3) aromatic amines.

(B1) The alkylphenol component (B1) is an alkylphenol of the formula:

[0118]

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Wherein R ⁴ is an alkyl group containing from 1 to about 24 carbon atoms, and a is an integer from 1 to 5. Preferably, R ⁴ is 4 to 18 carbon atoms, and most preferably contains 4 to 12 carbon atoms. R ⁴ can be either linear or branched;
Branched chains are preferred. Preferred values for a are integers from 1 to 4, with integers from 1 to 3 being most preferred. A particularly preferred value for a is 2. When a is not 5, it is preferred that the para position is vacant with respect to the OH group.

Mixtures of alkyl phenols can be used. Preferably, the phenol contains two or three
It is a butyl-substituted phenol containing a t-butyl group. a
When is 2, the t-butyl group occupies the 2,6-position, ie, the phenol is sterically hindered:

[0121]

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When a is 3, this t-butyl group is 2,4,6-
Occupy position.

(B2) Benzotriazole component (B2) is a benzotriazole compound of the following formula:

[0124]

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Here, R ⁵ is hydrogen or one to about 24
A straight or branched chain alkyl group containing up to and preferably 1 to 12 carbon atoms, most preferably 1 carbon atom. When R ⁵ has one carbon atom, the benzotriazole compound is a tolyltriazole of the formula:

[0126]

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The tolyltriazole is Cobratec TT-100
Available from Sherwin-Williams Chemical.

(B3) Aromatic amine component (B3) is at least one aromatic amine of the formula:

[0129]

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Where R ⁶ is

[0131]

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And R ⁷ and R ⁸ are independently
Hydrogen or an alkyl group containing from 1 to about 24 carbon atoms. Preferably, R ⁶ is

[0133]

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And R ⁷ and R ⁸ are from four to about
An alkyl group containing up to 18 carbon atoms. In a particularly preferred embodiment, component (B3) contains an alkylated diphenylamine (eg, a nonylated diphenylamine of the formula:

[0135]

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(C) Thickener This thickener is a metal salt formed by the reaction of (C1) a metal-based substance and (C2) a carboxylic acid or its ester.

(C1) Metal-based substance This metal-based substance (C1) is a metal oxide, a metal hydroxide, a metal carbonate or a metal bicarbonate. Metal hydroxides are preferred. This metal is an alkali metal or alkaline earth metal. Important alkali metals include lithium, sodium and potassium. Important alkaline earth metals include magnesium, calcium and barium. Preferred metal hydroxides include lithium hydroxide and calcium hydroxide.

(C2) Carboxylic acid or ester thereof The carboxylic acid or ester (C2) has the formula R ¹⁸ (COO
R ¹⁹ ) _n , wherein R ¹⁸ is an aliphatic or hydroxy-substituted aliphatic group containing 4 to 29 carbon atoms, R ¹⁹ is hydrogen, or 1 to 4 And n is an integer from 1 to 4. When R ¹⁸ is an aliphatic group, preferably, R ¹⁸ is from 12 to
It contains 24 carbon atoms and n is 1 or 2. A non-exhaustive list of these aliphatic groups includes: isomeric heptyl, isomeric heptenyl,
Isomeric octyl and octenyl, isomeric nonyl and nonenyl, isomeric dodecyl and dothecenyl, isomeric undecyl and undecenyl, isomeric tridecyl and tridecenyl, isomeric pentadecyl and pentadecenyl, isomeric heptadecyl and heptadecenyl, and isomeric nonadecyl and nonadecenyl. R ¹⁸ and R
^{When 19} are both aliphatic groups, R ¹⁹ is preferably a methyl group. When R ¹⁸ is an aliphatic group, R ¹⁹ is hydrogen, and n is 1, preferred carboxylic acids are caprylic, capric, lauric, myristic, palmitic, stearic, and oleic acids . R ¹⁸
When is an aliphatic group and n is 2, preferred dicarboxylic acids are azelaic acid and sebacic acid.

The R ¹⁸ group can also be a monohydroxy- or dihydroxy-substituted aliphatic group. When R ¹⁸ is a monohydroxy- or dihydroxy-substituted aliphatic group and R ¹⁹ is hydrogen, n is preferably equal to 1. This then gives rise to a monohydroxy- or dihydroxy-substituted monocarboxylic acid. Preferred monohydroxy-substituted aliphatic monocarboxylic acids include 6-
There are hydroxystearic acid, 12-hydroxystearic acid, 14-hydroxystearic acid, 16-hydroxystearic acid, ricinoleic acid, and 14-hydroxy-11-arachiic acid. A preferred dihydroxy-substituted monocarboxylic acid is 9,10-dihydroxystearic acid.

The metal base substance (C1) and the carboxylic acid or its ester for forming the thickener (C)
The reaction with (C2) is performed in a solution of the base oil (A) and the performance additive (B). The equivalent ratio of (C1) :( C2) is about 1: 0.70 to 1.10
The weight ratio of the base oil (A) to the sum of the metal base material (B1) and the carboxylic acid or its ester (B2) is 50:50 to 95: 5.

The reinforced grease composition of the present invention, that is, the components (A), (B) and (C) further comprises (D) a viscosity improver, (E)
It may contain a pour point depressant, or a mixture of (D) and (E).

(D) Viscosity improver This viscosity improver (D) is a hydrogenated block copolymer. It includes either normal block copolymers (ie, regular block copolymers) or random block copolymers. Considering this regular block copolymer, ie a normal block copolymer, it is generally only from conjugated dienes having from 4 to 10 carbon atoms, preferably from 4 to 6 carbon atoms. But from vinyl-substituted aromatic compounds having from 8 to 12 carbon atoms, preferably 8 or 9 carbon atoms.

Examples of vinyl-substituted aromatic compounds include styrene, α-methylstyrene, ortho-methylstyrene, meta-methylstyrene, para-methylstyrene and para-tertiary butylstyrene, with styrene being preferred.
Examples of such conjugated dienes include piperylene, 2,3-dimethyl-1,3-butadiene, chloroprene, isoprene and 1,3-butadiene, with isoprene and 1,3-butadiene being particularly preferred. Mixtures of such conjugated dienes are useful.

The normal block copolymer has from 2 to about 5, preferably 2 or 3, polymer blocks of the vinyl-substituted aromatic compound and the conjugated diene. At least one polymer block of the compound and at least one polymer block of the conjugated diene are present. This conjugated diene block is
It is hydrogenated, as described in further detail below.
The normal block copolymer may be a linear block copolymer, wherein one monomeric unit (block I) of a substantially longer sequence is a second ( (II), third (block III), fourth (block IV) or fifth (block V) monomeric units. For example, if a is a styrene monomeric unit and d is a conjugated diene monomeric unit, the triblock copolymer of these monomeric units is represented by the formula:

[0145]

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These copolymers can also be radial block copolymers, wherein the polymer blocks are radially linked as shown by the following formula:

[0147]

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In practice, the number of repeating monomer units contained in each polymer block usually exceeds about 500,
It may be less than about 500. The length of the sequence in a single block is determined by the physical properties of the block copolymer, such as the glass transition temperature and the polymer melting temperature.
Must be long enough to indicate

The content of vinyl-substituted aromatic compounds in these copolymers (ie, the total amount of vinyl-substituted aromatic blocks in the normal block copolymer) is typically
It ranges from about 20% to about 70% by weight, preferably from about 40% to about 60% by weight. Therefore, the content of aliphatic conjugated dienes of these copolymers (i.e., the content of total diene blocks) ranges from about 30% to about 80% by weight, preferably from about 40% to about 60% by weight. Range.

These normal block copolymers can be prepared by a conventional method well known in the art. Such a copolymer is usually prepared by anionic polymerization using, for example, an alkali metal hydrocarbon (for example, secondary butyllithium) as a polymerization catalyst.

Examples of suitable normal block copolymers shown above include Shellvis-40 and Shellvis-50, both of which are hydrogenated styrene-isoprene block copolymers manufactured by Shell Chemicals. is there.

This random block copolymer (which is
(Can be used separately or in combination with the normal block copolymer described above, or not used at all), it generally has one or more block polymer moieties therein. Defined as block copolymer. More specifically, the random block copolymer can be defined as having a variable number of a and d blocks of indeterminate length. These random copolymers can generally be prepared from conjugated dienes of the type described above, butadiene and isoprene, which are incorporated herein by reference, are preferred. The remaining monomers used to make this random block copolymer include vinyl-substituted aromatic compounds of the type set forth above, also incorporated herein by reference. . A suitable type of aromatic monomer is styrene. The random block copolymer can be prepared by feeding a mixture of monomers to the polymerization system simultaneously, rather than feeding a plurality of monomers in a continuous manner. The amounts by weight of the various blocks are the same as indicated above, ie, from about 20 to about 70 weight percent of the vinyl-substituted aromatic compound block, with 40 to 60 weight percent of such blocks being preferred. Therefore, the amount of this diene block is different. The number average molecular weight and weight average molecular weight of this random block copolymer are the same as those set forth above, and are therefore incorporated herein by reference. This random block copolymer is
It contains a substantial number of blocks of vinyl-substituted aromatic repeat units and / or a substantial number of blocks of conjugated diene repeat units and / or blocks of random or random tapered conjugated diene / vinyl-substituted aromatic compounds. These copolymers are also represented as A'-B'-A'-B'-, where A 'is a block of a vinyl-substituted aromatic compound and B' is a block of a conjugated diene. And the lengths of the A 'and B' blocks can vary widely and are much shorter than the A and B blocks of a normal block copolymer. The content of aromatic A blocks in the random block copolymer should preferably be in the range of about 15 to about 45% by weight, more preferably 25 to about 40% by weight.

Examples of such commercially available random block copolymers include various Glissovisc manufactured by BASF.
al block copolymers are included. A previously available random block copolymer was a Phil-Ad viscosity modifier manufactured by Phillips Petroleum.

Whether using regular (normal block) copolymers, or random block copolymers, or blends of both, they remove almost all of their olefinic double bonds. Before use in the present invention, it is hydrogenated. The way to do this hydrogenation is
It is well known to those skilled in the art and need not be described in detail. In summary, hydrogenation involves subjecting these copolymers to superatmospheric pressure in the presence of a metal catalyst (e.g., colloidal nickel, palladium on charcoal, etc.)
This is done by contacting with hydrogen.

In general, for reasons of oxidative stability, these block copolymers are more than about 5%, preferably about 0.5%, based on the total number of carbon-carbon covalent bonds present in the average molecule. Contains no residual olefinic unsaturation in excess of Such unsaturation can be measured by many methods well known to those skilled in the art (eg, infrared, NMR, etc.). Most preferably, these copolymers contain no unsaturation that can be detected by the analytical methods described above.

These block copolymers typically range from about 5,000 to about 1,000,000, preferably from about 30,0
It has a number average molecular weight (Mn) ranging from 00 to about 200,000. The weight average molecular weight of these copolymers is generally about 50,000
To about 500,000, preferably from about 30,000 to about 300,000
Range.

(E) Pour Point Depressants Pour point depressants (PPD) useful in the present invention include carboxy-containing interpolymers, where many of the carboxy groups are esterified and the remaining carboxy groups are , If any, have been neutralized by reaction with an amino compound), acrylate polymers, nitrogen-containing acrylate polymers, methylene-bound aromatics, and fumarate, vinyl esters and vinyl ethers. There are terpolymers.

Carboxy-Containing Interpolymer The PPD is an ester of a carboxy-containing interpolymer, wherein the interpolymer has a reduced specific viscosity of about 0.05 to about 2 and is derived from at least two monomers; One is a low molecular weight aliphatic olefin, styrene or substituted styrene, wherein the substituent is a hydrocarbyl group containing from 1 to about 18 carbon atoms and the other of the monomers is α,
β-unsaturated aliphatic acid, anhydride or ester thereof, wherein the ester is substantially free of titratable acidity, ie, at least 90% esterified, and its polymer structure Within the following pendant polar groups (a), (b) if necessary, and (c) if necessary
(Which is derived from the carbonyl group of the acid ester): (a) a relatively high molecular weight carboxylic acid having at least 8 aliphatic carbon atoms in the ester group An ester group, (b) a relatively low molecular weight carboxylic ester group having up to 7 aliphatic carbon atoms in the ester group, and optionally (c)
A carbonyl-amino group derived from an amino compound having one primary amino group or a secondary amino group, wherein the molar ratio of (a) :( b) is (1-20): 1, preferably (1-10): 1 where (a) :( b) :( c)
Is (50-100) :( 5-50) :( 0.1-15).

Regarding the size of the ester group, the ester group is represented by the following formula, and the number of carbon atoms in the ester group is the same as the number of carbon atoms in the carbonyl group and the number of carbon atoms in the ester group, ie, the (OR) group. It is pointed out that the total number is the sum of:

[0160]

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Optional elements of the ester may be derived from a particular amino compound, ie, a particular amino compound having a primary or secondary amino group and at least one monofunctional amino group therein. Is present. Such amino groups, when present in the mixed esters in the proportions described above, enhance the dispersibility of such esters in lubricant compositions and additive concentrates for lubricant compositions.

Yet another essential element of this mixed ester is the degree of esterification, which is related to the degree of neutralization by converting the non-esterified carboxy groups of the carboxy-containing interpolymer to any amino-containing groups. . For convenience, the relative proportions of the high molecular weight ester group, the low molecular weight ester group, and the amino group are (50
100100) :( 55050) :( 0.1〜15). The preferred ratio is (70-85) :( 15-30) :( 3-4). The bond described as a carbonyl-amino group can be an imide, amide or amidine, and as long as such a bond is considered in the present invention, the term "carbonylamino" is used for purposes of defining the inventive concept. It should be noted that this is considered to be a useful and general expression useful above. In a particularly advantageous embodiment of the invention, such a bond is an imide or predominantly an imide.

Yet another important factor in the mixed ester is the molecular weight of the carboxy-containing interpolymer. For convenience, the molecular weight is represented by the "reduced specific viscosity" of the interpolymer, which is a widely recognized measure of the molecular size of a polymeric material. As used herein, this reduced specific viscosity (abbreviated as RSV)
Is a value obtained according to the following equation:

[0164]

(Equation 1) Here, the relative viscosity is determined by measuring the viscosity of a solution of 1 gram of the interpolymer in 10 ml of acetone and the viscosity of acetone at 30 ° C. ± 0.02 ° C. using a dilution viscometer. For the calculation according to the above equation, the concentration is
It is adjusted to 0.4 g of interpolymer per 100 ml of acetone. A more detailed discussion of reduced specific viscosity (also known as specific viscosity), and its relationship to the average molecular weight of the interpolymer, can be found in Paul J. Flory's P.
It is described in rinciples of Polymer Chemistry (1953 edition), page 308 et seq .

For this mixed ester, although interpolymers having a reduced specific viscosity of about 0.05 to about 2 are contemplated, preferred interpolymers are those having a reduced specific viscosity of about 0.1 to about 1. In most cases, about 0.1 to about
Interpolymers having a reduced specific viscosity of 0.8 are particularly preferred.

For commercial and economic reasons, as well as from a utility standpoint, high molecular weight ester groups have from 8 to 24 aliphatic carbon atoms and low molecular weight ester groups have from 3 to Esters having 5 carbon atoms and wherein the carbonylamino group is derived from a primary aminoalkyl-substituted tertiary amine, especially a heterocyclic amine, are preferred. High molecular weight carboxylic ester groups, ie, ester groups
Particular examples of (OR) groups of (i.e.,-(O) (OR)) include heptyloxy, isooctyloxy, decyloxy, dodecyloxy, tridecyloxy, tetradecyloxy,
Pentadecyloxy, octadecyloxy, eicosyloxy, tricosyloxy, tetracosyloxy and the like are included. Specific examples of low molecular weight groups include methoxy, ethoxy, n-propyloxy, isopropyloxy, n-butyloxy, sec-butyloxy, isobutyloxy, n-butyloxy
Pentyloxy, neopentyloxy, n-hexyloxy, cyclohexyloxy, xylopentyloxy, 2-
Methylbutyl-1-oxy, 2,3-dimethylbutyl-1-oxy and the like are included. In most cases, suitable sized alkoxy groups will contain preferred high and low molecular weight ester groups. A polar substituent may be present in such an ester group. Examples of polar substituents include chloro, bromo, ether, nitro and the like.

Examples of the carbonylamino group include one primary amino group or secondary amino group and at least one monofunctional amino group (for example, tertiary amino group or heterocyclic amino group). And those derived from amino compounds. Such compounds may therefore be tertiary amino-substituted primary or secondary amines, or other substituted primary or secondary amines, wherein the substituted Groups are pyrrole, pyrrolidone, caprolactam, oxazolidone, oxazole,
Thiazole, pyrazole, pyrazoline, imidazole,
It is derived from imidazoline, thiazine, oxazine, diazine, oxycarbamyl, thiocarbamyl, uracil, hydantoin, thiohydantoin, guanidine, urea, sulfonamide, phosphoramide, phenolthiazine, amidine and the like. Examples of such amino compounds include dimethylamino-ethylamine, dibutylamino-
Ethylamine, 3-dimethylamino-1-propylamine, 4
-Methylethylamino-1-butylamine, pyridyl-ethylamine, N-morpholino-ethylamine, tetrahydropyridyl-ethylamine, bis- (dimethylamino) propylamine, bis- (diethylamino) ethylamine, N,
N-dimethyl-p-phenylenediamine, piperidyl-ethylamine, 1-aminoethylpyrazole, 1- (methylamino) pyrazoline, 1-methyl-4-aminooctylpyrazole, 1-aminobutylimidazole, 4-aminoethylthiazole, 2 -Aminoethylpyridine, ortho-amino-ethyl-N, N-dimethylbenzenesulfamide, N-aminoethylphenothiazine, N-aminoethylacetamidine,
1-aminophenyl-2-aminoethylpyridine, N-methyl-
N-aminoethyl-S-ethyl-dithiocarbamate and the like are included. Preferred amino compounds include N-aminoalkyl substituted morpholines (eg, aminopropyl morpholine). In most cases, this amino compound has only one primary or secondary amino group.
(Preferably, at least one tertiary amino group). The tertiary amino group is preferably
It is a heterocyclic amino group. In some cases, the amino compound may contain up to about six amino groups, but in most cases, one primary amino group and one or two tertiary amino groups It contains. The amino compound can be an aromatic or aliphatic amine, preferably a heterocyclic amine (eg, amino-alkyl-substituted morpholine, piperazine, pyridine, benzopyrrole, quinoline, pyrrole, etc.). These are usually amines having 4 to about 30 carbon atoms, preferably 4 to about 12 carbon atoms. Polar substituents can likewise be present in the polyamine.

The carboxy-containing interpolymer mainly includes an α, β-unsaturated acid or its anhydride (eg, maleic anhydride or itaconic anhydride) and an olefin (aromatic or aliphatic) (eg, ethylene, Interpolymers with propylene, isobutene or styrene, or substituted styrene, where the substituent is a hydrocarbyl group containing from 1 to about 18 carbon atoms. Styrene-maleic anhydride interpolymers are particularly useful. These are obtained by polymerizing equimolar amounts of styrene and maleic anhydride with or without one or more other interpolymerizable comonomers. Instead of styrene, aliphatic olefins (e.g.,
Ethylene, propylene or isobutene). Instead of maleic anhydride, acrylic acid or methacrylic acid or esters thereof may be used. Such interpolymers are well known in the art,
There is no need to describe in detail here. When an interpolymerizable comonomer is considered, it may be in a relatively small proportion, i.e., an olefin (e.g., styrene) or an alpha, beta-unsaturated acid or anhydride (e.g., maleic anhydride). Less than about 0.3 mole, usually less than about 0.15 mole, per mole of Various methods for interpolymerizing styrene and maleic anhydride are well known in the art,
There is no need to discuss in detail here. Examples of this interpolymerizable comonomer include a vinyl monomer.
(Eg, vinyl acetate, acrylonitrile, methyl acrylate, methyl methacrylate, acrylic acid, vinyl methyl ether, vinyl ethyl ether, vinyl chloride, isobutene, etc.).

The nitrogen-containing ester of this mixed ester is
Most conveniently, the carboxy-containing interpolymer is prepared by first 100% esterifying the carboxy-containing interpolymer with a relatively high molecular weight alcohol and a relatively low molecular weight alcohol. When this optional (c) is used, the high and low molecular weight alcohols comprise at least about 50% and about 98% of the interpolymer.
The following carboxy groups are used to convert to ester groups, and the remaining carboxy groups are then neutralized with an amino compound as described above. In order to incorporate a suitable amount of two alcohol groups into the interpolymer, the ratio of high molecular weight alcohol to low molecular weight alcohol used in this method, on a molar basis, ranges from about 2: 1 to about 9: 1. Should be. In most cases, this ratio is about 2.5:
1 to about 5: 1. In this method, more than one high or low molecular weight alcohol may be used. Also, commercially available alcohol mixtures (e.g., so-called oxo alcohols, which are composed, for example, of alcohol mixtures having 8 to about 24 carbon atoms) can be used. Particularly useful classes of alcohol include:
There are commercially available alcohols or mixtures of alcohols, including decyl alcohol, dodecyl alcohol, tridecyl alcohol, tetradecyl alcohol, pentadecyl alcohol, hexadecyl alcohol, heptadecyl alcohol and octadecyl alcohol. Examples of other alcohols useful in this method include those that upon esterification yield the above exemplified ester groups.

The degree of esterification was, as indicated above,
The conversion of carboxy groups to ester groups in the interpolymer can range from about 50% to about 98%. In a preferred embodiment, the degree of esterification ranges from about 75% to about 95%.

[0171] The esterification can be accomplished by simply heating the carboxy-containing interpolymer and alcohol under conditions typical of performing esterification. Such conditions typically include, for example, a temperature of at least about 80 ° C, preferably a temperature of about 150 ° C to about 350 ° C, provided that the temperature is below the decomposition point of the reaction mixture, and And the removal of water in the esterification as the reaction proceeds. These conditions include:
Use of excess alcohol reactants to promote esterification, solvents or diluents (e.g., mineral oil, toluene, benzene, xylene, etc.) and esterification catalysts (e.g.,
Toluene sulfonic acid, sulfuric acid, aluminum chloride, boron trifluoride-triethylamine, hydrochloric acid, ammonium sulfate, phosphoric acid, sodium methoxide, etc.). These conditions and their modifications are well known in the art.

A particularly desirable method of performing the esterification is to first react the carboxy-containing interpolymer with a relatively high molecular weight alcohol,
Reacting the partially esterified interpolymer with a relatively low molecular weight alcohol is included. An alternative to this method involves initiating esterification with the relatively high molecular weight alcohol, and prior to completion of such esterification, the reaction to achieve mixed esterification. This relatively low molecular weight alcohol is introduced into the mass. In any event, by the two-step esterification process, the carboxy-containing interpolymer is first esterified with this relatively high molecular weight alcohol to convert from about 50% to about 75% of the carboxy groups to ester groups. And then esterified with this relatively low molecular weight alcohol to ultimately achieve the desired degree of esterification, resulting in a product having exceptionally useful viscosity properties. Was.

The esterified interpolymer is
If desired, the interpolymer may be treated with an amino compound in an amount to neutralize substantially all non-esterified carboxy groups. The neutralization is preferably performed at a temperature of at least about 80 ° C., often at a temperature of about 120 ° C. to about 300 ° C., provided that this temperature does not exceed the decomposition point of the reaction mass. In most cases, this neutralization temperature will be between about 150 ° C and 250 ° C.
To ensure substantially complete neutralization, a slight excess of stoichiometric amino compound is often desirable. That is, less than about 2% of the carboxy groups initially present in the interpolymer remain unneutralized.

[0174]

The following examples illustrate the preparation of the mixed esters of the present invention. Unless otherwise indicated, all parts and percentages are by weight.

Example (E-1) A benzene-toluene solution of styrene (16.3 parts by weight) and maleic anhydride (12.9 parts) (270 parts; the weight ratio of benzene: toluene is 66.5: 33.5) was prepared. , This solution
Contact with a catalyst solution (prepared by dissolving 70% benzoyl peroxide (0.42 parts) in a similar benzene-toluene mixture (2.7 parts) under a nitrogen atmosphere at 86 ° C. for 8 hours. Thereby, a styrene-maleic acid interpolymer is obtained. The resulting product is a thick slurry of the interpolymer in the solvent mixture. Mineral oil (141 parts) is added to the slurry while distilling off the solvent mixture at 150 ° C. and then at 150 ° C./200 mm. Hg. The stripped mineral oil-interpolymer slurry
(This interpolymer has a reduced specific viscosity of 0.72)
To 209 parts, toluene (25.2 parts), n-butyl alcohol (4.8
Parts), a commercial alcohol consisting essentially of a primary alcohol having 12 to 18 carbon atoms (56.6 parts) and a commercial alcohol consisting of a primary alcohol having 8 to 10 carbon atoms ( 10 parts), and 96% was added to the resulting mixture.
Add sulfuric acid (2.3 parts). The mixture is then brought to 150 ° C.
Heat at 160 ° C. for 20 hours, after which the water is distilled off. Add an additional amount of n-butyl alcohol (3.
And the esterification is continued until 95% of the carboxy groups of the polymer are esterified. To this esterified interpolymer was then added aminopropylmorpholine (3.71 parts; 10% excess of the stoichiometric amount required to neutralize the remaining free carboxy groups),
The resulting mixture is heated to 150 ° C. to 160 ° C./10 mm.Hg to distill off toluene and all other volatile components.
Add this stripped product to an additional amount of mineral oil (12 parts)
And filter. The filtrate is a mineral oil solution of a nitrogen-containing mixed ester having a nitrogen content of 0.16-0.17%.

Example (E-2) Esterification was carried out in two stages, the first being a styrene reaction with a commercially available alcohol having 8 to 18 carbon atoms.
Esterification of the maleic acid interpolymer;
Except that the step is the subsequent esterification of this interpolymer with n-butyl alcohol,
Follow the method of 1).

Example (E-3) First, a styrene-maleic acid interpolymer was converted to a commercially available styrene-maleic acid copolymer having 8 to 18 carbon atoms until 70% of the carboxyl groups of the interpolymer were converted to ester groups. Except that it is esterified with an alcohol and then continues with the unreacted commercial alcohol and n-butyl alcohol until 95% of the carboxyl groups of the interpolymer have been converted to ester groups. Following the method of Example (E-1).

Example (E-4) Styrene (416 parts), maleic anhydride (392 parts), benzene (2 parts)
153 parts) and toluene (5025 parts) in the presence of benzoyl peroxide (1.2 parts) at 65 ° C. to 106 ° C. to prepare an interpolymer, except that an interpolymer is prepared. Follow the method in -1). (The resulting interpolymer has a reduced specific viscosity of 0.45).

Example (E-5) Styrene (416 parts), maleic anhydride (392 parts), benzene (6 parts)
(101 parts) and toluene (2310 parts) in the presence of benzoyl peroxide (1.2 parts) at 78 ° C to 92 ° C, to obtain a styrene-maleic anhydride, except for obtaining a styrene-maleic anhydride. Follow the method in E-1). (The resulting interpolymer has a reduced specific viscosity of 0.91).

Example E-6 The procedure of Example (E-1) is followed, except that styrene - maleic anhydride is prepared by the following method: Maleic anhydride (392 parts) is dissolved in benzene (6870 parts) Let it. To this mixture is added styrene (416 parts) at 76 ° C., followed by benzoyl peroxide (1.2 parts). The polymerization mixture is mixed with 80-8
Maintain at 2 ° C. for about 5 hours. (The resulting interpolymer is
With a reduced specific viscosity of 1.24).

Example (E-7) As a polymerization solvent, acetone (1340 parts) was used instead of benzene.
And using the azobisisobutyronitrile (0.3 part) instead of benzoyl peroxide as the polymerization catalyst, according to the method of Example (E-1).

Example (E-8) Interpolymer of styrene and maleic anhydride (0.8%)
6 carboxyl equivalents) (prepared from an equimolar mixture of styrene and maleic anhydride, having a reduced specific viscosity of 0.69)
Is mixed with mineral oil to form a slurry, then a commercial alcohol mixture (0.77 moles) at 150-160 ° C. in the presence of a catalytic amount of sulfuric acid until about 70% of the carboxyl groups are converted to ester groups. Composed of primary alcohols having 8 to 18 carbon atoms).
This partially esterified interpolymer is then
N-butyl alcohol (0.31 mol) until 95% of the carboxyl groups of the interpolymer are converted to mixed ester groups
To further esterify. The esterified interpolymer is then combined with aminopropyl morpholine (the interpolymer) at 150-160 ° C. until the resulting product is substantially neutral (acid number 1 for phenolphthalein indicator). (A slight excess over the stoichiometric amount to neutralize the free carboxyl groups of the polymer). The resulting product is mixed with mineral oil to form an oil solution containing 34% polymer product.

The compounds of Examples (E-1) to (E-8) are prepared using mineral oil as diluent. All or part of the mineral oil may be replaced by the base oil (A) as shown in Examples (E-9) to (E-11). A preferred triglyceride oil is high oleic sunflower oil.

Example (E-9) A toluene ( 12 liter ) four-necked flask is charged with 3621 parts of the interpolymer of Example (E-8) as a toluene slurry. The proportion of toluene is about 76%. Begin stirring and add 933 parts (4.3 equivalents) of Alfol 1218 alcohol and 1370 parts of xylene. The contents are heated and toluene is removed by distillation. While continuing to remove toluene,
Additional xylene is added in portions of 500, 500, 300 and 300 parts. The purpose is to replace low boiling toluene with high boiling xylene. When the temperature of 140 ° C. is reached, the removal of the solvent is stopped. The flask is then provided with an addition funnel and the condenser is brought to reflux.
At 140 ° C. in about 20 minutes, 23.6 parts (0.17 equivalents) of methanesulfonic acid in 432 parts (3 equivalents) of Alfol 810 alcohol are added.
The contents are stirred overnight at reflux while collecting water with a Dean Stark trap. Then 185 parts (2.5 equivalents) of n-butanol containing 3.0 parts (0.02 equivalents) of methanesulfonic acid are added. This addition takes place over a period of 60 minutes. The contents are maintained at reflux for 8 hours and then additional
60 parts (0.8 equivalent) of n-butanol are added and the contents are refluxed overnight. At 142 ° C. for 60 minutes, 49.5 parts (0.34 equivalents) of aminopropylmorpholine are added. After 2 hours of reflux,
13.6 parts (0.17 equivalents) of a 50% aqueous sodium hydroxide solution are added over 60 minutes, and after stirring for a further 60 minutes, 17 parts of alkylated phenol are added.

To a one liter flask is added 495 parts of the above esterified product. Heat the contents to 140 ° C,
Add 337 parts of Sunyl® 80 oil. 1 per hour
Solvent is removed at 155 ° C. while blowing in nitrogen at the rate of cubic feet. Final stripping conditions are 155 ° C
And 20 mm Hg. Using diatomaceous earth at 100 ° C,
The contents are filtered. The filtrate is a vegetable oil solution of a nitrogen-containing mixed ester having a nitrogen content of 0.14%.

Examples (E-10) and (E-11) use an interpolymerizable monomer as part of the carboxy-containing interpolymer.

Example (E-10) One mole of each of maleic anhydride and styrene and 0.05 mole of methyl methacrylate were added to benzoyl peroxide at 75 to 95 ° C.
(1.5 parts) and polymerized in toluene. The resulting interpolymer has a reduced specific viscosity of 0.13 and is a 12% slurry in toluene. In a 2 liter four-necked flask, add 68 parts (0.25 equivalent) of oleyl alcohol, 55 parts
Parts (0.25 equivalents) Neodol 45, 55 parts (0.25 equivalents) Alfol 121
868 parts (1 equivalent) of the polymer are added along with 8 and 36 parts (0.25 equivalent) of Alfol 8-10. The contents are heated to 115 ° C. and 2 parts (0.02 mol) of methanesulfonic acid are added. 2
After a reaction period of time, the toluene is distilled off. With a phenolphthalein neutralization number of 18.7 (indicating 89% esterification), n-
15 parts of butanol (0.20 eq.) Are added dropwise over 5 hours. Its neutralization number / esterification level is 14.0 / 92.5
%. Next, 1.6 parts of a 50% aqueous sodium hydroxide solution
(0.02 mol) is added to neutralize the catalyst. This is followed by the addition of 5.5 parts (0.038 equivalents) of aminopropylmorpholine and 400 parts of Sunyl® 80 oil. The contents are vacuum stripped to 15 millimeters of mercury at 100 ° C. and filtered using a diatomaceous earth filter aid. The filtrate is a product containing 0.18 percent nitrogen and 54.9 percent Sunyl® 80 oil.

The following examples are identical except that different alcohols are used at different levels and in different addition orders.
This is similar to the embodiment (E-10).

Example (E-11 ) The polymer of Example (E-10) was placed in a 2 liter four-necked flask.
868 parts (1 equivalent), isobutyl alcohol 9.25 parts (0.125 equivalent), oleyl alcohol 33.8 parts (0.125 equivalent), 2-methyl
1-butanol, 3-methyl-1-butanol and 1-pentanol each 11 parts (0.125 equivalent), hexyl alcohol 23.4 parts
(0.125 eq), and 16.25 parts of each of 1-octanol and 2-octanol (0.125 eq). At 110 ° C., 2 parts (0.02 mol) of methanesulfonic acid are added. After one hour, the toluene is distilled off, and when the distillation is complete, the neutralization number / esterification level is 62.5 / 70 percent. Addition of 31.2 parts (0.43 equivalents) of n-butanol dropwise at 140 ° C. over 28 hours gives this neutralization number / esterification level of 36.0 / 79.3 percent. At 120 ° C., 0.3 part of methanesulfonic acid (0.0
3 mol), followed by 20.4 parts of hexyl alcohol (0.2
(0 equivalent). After esterification, this neutralization number / esterification level will be 10.5 / 95 percent. Then 50%
1.9 parts (0.023 mol) of sodium hydroxide were added, followed by 5.
9 parts (0.04 equivalents) of aminopropylmorpholine, and 400
Add some Sunyl® 80 oil. Upon filtration of these contents, the product has a nitrogen analysis of 0.18 percent.

Acrylate Polymer In another aspect, component (E) is at least one hydrocarbon soluble acrylate polymer of the formula:

[0191]

Embedded image

Where R ⁹ is hydrogen or a lower alkyl group containing 1 to about 4 carbon atoms, R ¹⁰ is an alkyl group containing about 4 to about 24 carbon atoms, cyclo A mixture of alkyl or aromatic groups, and x is an integer that gives the acrylate polymer a weight average molecular weight (Mw) of about 5,000 to about 1,000,000.

Preferably, R ⁹ is a methyl group or an ethyl group, and more preferably, a methyl group. R
¹⁰ is primarily a mixture of alkyl groups containing from 4 to about 18 carbon atoms. In one embodiment, the weight average molecular weight of the acrylate polymer is from about 50,000 to about 500,000, and in another embodiment, the molecular weight of the polymer is from 100,000 to about 500,000 and 300,000 to about 50,000.
It can be 0,000.

The alkyl group R which can be contained in the polymer of the present invention
^Ten specific examples include, for example, n-butyl, octyl, decyl, dodecyl, tridecyl, octadecyl, hexadecyl. The mixture of alkyl groups may be varied as long as the resulting polymer is hydrocarbon soluble.

The following examples illustrate the preparation of the acrylate polymers of the present invention. All parts and percentages are by weight unless otherwise indicated.

Example (E-12) Lauryl methacrylate was placed in a 2 liter four-necked flask.
50.8 parts (0.20 mol), 44.4 parts of isobornyl methacrylate
(0.20 mol), 38.4 parts of 2-phenoxyethyl acrylate (0.2
0 mol), 37.6 parts (0.20 mol) of 2-ethylhexyl acrylate, 45.2 parts (0.20 mol) of isodecyl methacrylate and 500 parts of toluene. At 100 ° C, in 20 parts of toluene
One part of Vazo® 67 (2,2′-azobis (2-methylbutyronitrile)) is added over 7 hours. This reaction is 100
C. for 16 hours, then raise the temperature to 120.degree. C. to remove the toluene and add 216 parts of Sunyl.RTM. 80 oil. The volatiles are removed by vacuum distillation at 140 ° C. and 20 millimeters of mercury. Filtration of these contents gives the desired product.

Example (E-13) Lauryl methacrylate was placed in a 2 liter four-necked flask.
38.1 parts (0.15 mol), 48.6 parts of stearyl acrylate (0.15
Mol), 28.2 parts of 2-ethylhexyl methacrylate (0.15 mol), 25.5 parts of tetrahydrofurfuryl methacrylate (0.15 mol)
Mol), 33.9 parts (0.15 mol) of isodecyl methacrylate and 500 parts of toluene. At 100 ° C., Vazo® 67 (1 part) in 20 parts of toluene is added dropwise over 6 hours.
After the addition is complete, the reaction mixture is kept at 100 ° C. for 15.5 hours, the toluene is distilled off and 174 parts of Sunyl® 80 oil are added. At 140 ° C and 20 ° C
Vacuum stripping with millimeters of mercury and filtration gives the desired product.

Examples of commercially available methacrylate polymers found to be useful in the present invention include Rohm and H.
Some are sold by aas under the trade name “Acryloid 702”, where R ¹⁰ is primarily a mixture of n-butyl, tridecyl and octadecyl groups. The weight average molecular weight (Mw) of the polymer is about 404,000 and the number average molecular weight (Mn) is about 118,000. Other commercially available methacrylate polymers useful in the present invention are Rohm
and Haas available under the trade name "Acryloid 954"
Here, R ¹⁰ is mainly a mixture of n-butyl, decyl, tridecyl, octadecyl and tetradecyl groups. Acryloid 954 has a weight average molecular weight of about 440,
000 and its number average molecular weight is
It is about 111,000. Each of these commercially available methacrylate polymers is sold in the form of a concentrate of about 40% by weight of the polymer in a pale mineral lubricating oil base. When this polymer is identified by its trade name, the amount of substance added is intended to represent the amount of commercially available Acryloid substance including oil.

Other commercially available polymethacrylates are:
Acryloid 1253, Acryloid from Rohm and Haas Company
1265, Acryloid 1263, Acryloid 1267, Rohm Gm
From bH, Viscoplex 0-410, Viscoplex 10-930, Visco
As plex 5029, Societe Francaise D'Organo-Synthe
From se, Garbacryl T-84, Garbacryl T-78S, Tex
Available from aco as TLA 233, TLA 5010 and TC 10124. Some of these polymethacrylates can be PMA / OCP (olefin copolymer) type polymers.

Methylene-Bound Aromatic Compounds Another PPD useful in the present invention is a mixture of compounds having the following general structure:

[0201]

Embedded image

Here, Ar, Ar ′ and Ar ″ independently represent
An aromatic moiety containing 1 to 3 aromatic rings, each aromatic moiety being substituted with 0 to 3 substituents (a preferred aromatic precursor is naphthalene), R ¹¹ and R
¹² is independently linear or branched alkylene containing from 1 to 100 carbon atoms, n is from 0 to 1000, n 'is 0 or 1, and X is Hydrocarbylene groups containing from 1 to 24 carbon atoms.

The PPD has a broad molecular weight range (generally about
300 to about 300,000, preferably about 300 to about 10,000). The molecular weight of the compounds in the compositions of the present invention can vary from the molecular weight of a single unsubstituted benzene to a polymer of 1000 monomers of a trisubstituted naphthalene linked to an alkylene containing about 100 carbon atoms. Wherein the substituent of the naphthalene contains 1 to 50 carbon atoms.

The substituents on the aromatic moiety are obtained from olefins and / or chlorinated hydrocarbons.

Useful olefins include 1-octene, 1-decene, and chain lengths C ₁₂ , C ₁₄ , C _16-18 , C _15-20 , C _20-24 ,
C _24-28 α-olefins. More preferably, the process is carried out using an olefin which is a mixture of the above compounds. Suitable examples include C _15-20 decomposed wax olefins, or 1-octene and C
There is a mixture of _16-18 alpha olefins.

The chlorinated hydrocarbon may contain 1 to 50 carbon atoms and about 2% to about 84% by weight of chlorine. Preferred chlorinated hydrocarbons are obtained by chlorinating _C18-30 chain length slack wax or paraffin wax to contain 5 to 50% by weight of chlorine. Particularly preferred chlorinated hydrocarbons are those containing about 2.5 chlorine / 24 carbon atoms and having 1 to about 24 carbon atoms.

Although Ar, Ar 'and Ar "can be aromatic compounds containing one to three aromatic rings, it is preferred that Ar, Ar' and Ar" are all the same. Furthermore, A
r, Ar 'and Ar "are fused benzene rings, ie, when two or three benzene rings are present, the adjacent rings preferably share two carbon atoms. Most preferably, Ar, Ar 'and Ar "are all derived from naphthalene.

Aromatic compounds which may be precursors of Ar, Ar 'and Ar "include benzene, biphenyl, diphenylmethane, triphenylmethane, aniline, diphenylamine, diphenylether, phenol, naphthalene, anthracene and phenanthrene. Is particularly preferred.

Although the aromatic groups of the above general formula can contain from 0 to 3 substituents, this composition comprises one or two substituents.
It contains a compound having two substituents, and preferably includes a compound having two substituents. These substituents can be derived from olefins (preferably α-olefins containing 8 to 30 carbon atoms) or
It can be derived from chlorinated hydrocarbons containing from 1 to 50 carbon atoms (preferably chlorinated hydrocarbons derived from hydrocarbon waxes containing from 22 to 26 carbon atoms). Additionally or alternatively, the olefins and / or chlorinated hydrocarbons can form alkylene linking groups (R ¹¹ and R ¹² groups) of the general structural formula. The compositions of the present invention can contain the following compounds: in which each naphthalene group has one alkyl group containing 16 to 18 carbon atoms, and about 24 carbon atoms each. Replaced by one derived from a chlorinated hydrocarbon containing about 24 carbon atoms with 2.5 carbon atoms.

The desired materials are alkylated naphthalenes, coupled and crosslinked naphthalenes,
A mixture of products containing oligomers and dihydrohalogenated waxes. The Mw distribution of the final product is a further useful feature of the final product. Useful Mw range is 300-3
00,000. A further useful Mw range is 300 to 112,000. The preferred distribution is between 400 and 112,000. The most useful distribution is from about 400 to about 112,000.

A disclosure of how to prepare a methylene-linked aromatic compound can be found in US Pat. No. 4,753,745.
Found in the issue. A typical method for preparing a methylene-linked aromatic compound is disclosed in Example E-14. U.S. Pat. No. 4,753,745 is incorporated herein by reference for its disclosure of this methylene linked aromatic compound.

Example E-14 Naphthalene is mixed with CH ₂ Cl ₂ (7 parts) and AlCl ₃ (0.2 parts). The reaction mixture is added to a chlorinated hydrocarbon
(2.7 parts) are added slowly. The reaction mixture is held at room temperature for 5 hours or until the release of HCl is complete. The mixture is then cooled to about 5 ° C and 7.3 parts of the α-olefin mixture are added over 2 hours while maintaining the temperature of the reaction mixture between 0 ° C and 10 ° C.

The catalyst is decomposed by careful addition of 0.8 parts of a 50% aqueous NaOH solution. The aqueous phase was separated and the organic phase was purged with N _2, and 140 ° C. and 3 mmHg
Heat to remove this volatile material. Filtration of the residue gives 97% of the theoretical yield (by weight) of the product.

The nitrogen-containing polyacrylate component (E) can also be a nitrogen-containing polyacrylate prepared by reacting an acrylate of the following formula with a nitrogen-containing compound:

[0215]

Embedded image

Here, R ¹³ is hydrogen or 1 to about 8
An alkyl group containing 6 carbon atoms and R ¹⁴
Is an alkyl, cycloalkyl or aromatic group containing from 4 to about 24 carbon atoms. For each mole of the acrylate, the nitrogen-containing compound is 0.001 to
1.0 mole is used. The reaction is performed at a temperature from 50 ° C to about 250 ° C. Non-limiting examples of nitrogen-containing compounds include 4-vinylpyridine, 2-vinylpyridine, 2-N-morpholinoethyl acrylate, N, N-dimethylaminoethyl acrylate, and N, N-dimethylamino methacrylate. There is propyl.

The following examples illustrate the preparation of nitrogen-containing polymethacrylates. All parts and percentages are by weight unless otherwise indicated.

Example (E-15) Lauryl methacrylate was placed in a 2 liter four-necked flask.
50.8 parts (0.2 mol), 44.4 parts of isobornyl methacrylate (0.
20 mol), 38.4 parts (0.20 mol) of 2-phenoxyethyl acrylate, 37.6 parts (0.20 mol) of 2-ethylhexyl acrylate,
45.2 parts (0.20 mol) of isodecyl methacrylate, 21 parts (0.20 mol) of 4-vinylpyridine and 500 parts of toluene are added. 1
At 00 ° C., 1 part of Vazo 67 in 20 parts of toluene is added dropwise over 8 hours. Increase this temperature to 100 ° C for another 20
After maintaining the time, add 0.5 parts additional Vazo in 10 parts toluene.
Add 67 in 3 hours. The toluene is then removed by distillation, 235 parts of Sunyl® 80 are added, and the contents are vacuum stripped at 140 ° C. to 25 millimeters of mercury. Filtration of these contents yields nitrogen 0.
A product having 71 percent is obtained.

A small number of companies producing nitrogen-containing polyacrylates include Rohm and Haas, Rohm GmbH, Te
xaco, Albright & Wilson, Societe Francaise and D'O
There is rgano-Synthese (SFOS).

Fumaric acid esters, vinyl esters and
Terpolymers of Vinyl Ethers The final PPDs useful in the present invention are terpolymers of dialkyl fumarate, vinyl esters of fatty acids and alkyl vinyl ethers. The terpolymer has a specific viscosity of 0.090-0.800, measured at 30 ° C., in a solution of 5 grams of the terpolymer per 100 ml of benzene, and at a temperature of 25 ° C.-150 ° C. , The following (a) 1 mol, and
By polymerizing 0.5 to 1 mol of a mixture of (b) and (c): (a) fumaric acid ester of the formula:

[0221]

Embedded image

Wherein R ¹⁵ is an alkyl group containing 10 to 18 carbon atoms; (b) a vinyl ester of the following formula:

[0223]

Embedded image

Wherein R ¹⁶ is an alkyl group containing 2 to 10 carbon atoms; (c) a vinyl ether of the following formula:

[0225]

Embedded image

Here, R ¹⁷ is an alkyl group containing 1 to 10 carbon atoms, and the molar ratio of (b) to (c) in the mixture is 9: 1 to 1: 9. Range.

The dialkyl fumarate useful in the preparation of this terpolymer is readily obtained by esterification of fumaric acid with an alcohol R ¹⁵ OH, where R ¹⁵ is about 10 to 1
It contains 8 carbon atoms, preferably 12 to 14 carbon atoms. Useful esterification conditions are used. However, the method of preparing this ester is not important,
Any of the general methods for producing the desired ester (eg, transesterification) can be used.

As noted above, alcohols useful in the preparation of the dialkyl fumarate include those having 10 to 18 carbon atoms (eg, decyl (C ₁₀ ) alcohol, dodecyl (C ₁₂ ) alcohol , Tetradecyl (C ₁₄ ) alcohol,
Hexadecyl (C ₁₇ ) alcohol, and octadecyl (C
₁₈ ) alcohol). In addition to the individual alcohols, mixtures of two or more alcohols having an average number of carbon atoms of from about 10 to about 18, preferably from about 12 to 14, are also provided in the preparation of the dialkyl fumarate. Can be used for
Suitable commercially available mixed alcohols include those obtained by hydrogenation of natural oils (eg, coconut oil and tallow).
One preferred commercially available alcohol mixture consists of 2% decyl alcohol, 65% dodecyl alcohol, 26% tetradecyl alcohol, and 7% hexadecyl alcohol. Alcohols or alcohol mixtures containing on average 12 to 14 carbon atoms are particularly preferred. This is because the terpolymer obtained from dialkyl fumarate containing 12 to 14 carbon atoms in the alkyl group has excellent oil solubility and pour point depressing properties.

A second reactant useful in the preparation of the terpolymer is a vinyl ester of a fatty acid, where the
R ¹⁶ groups, about 2 to 10 carbon atoms, preferably 2 to 6 carbon atoms, and most preferably contain 2 carbon atoms. Examples of such vinyl esters include vinyl acetate, vinyl butyrate, vinyl hexanoate, and vinyl octanoate. While any of the above esters may be useful, vinyl acetate is preferred.

A third reactant useful in the preparation of the terpolymer is an alkyl vinyl ether, where the alkyl group R ¹⁷ contains about 1 to 10 carbon atoms. Examples of such vinyl ethers include methyl vinyl ether, ethyl vinyl ether, isobutyl vinyl ether, and n-butyl vinyl ether.
Preferably, R ¹⁷ is an ethyl group, and the preferred vinyl ether is ethyl vinyl ether.

Generally, in this monomer mixture, a mixture of the vinyl ester of (b) and the alkyl vinyl ether of (c) is about 0.5 per mole of the dialkyl fumarate of (a).
Used in about 1 mole. The preferred molar ratio of (a) to the mixture of (b) and (c) is 1: 1. This is because the terpolymer obtained from such a mixture is characterized by excellent oil solubility. The molar ratio of vinyl ester (b) to vinyl ether (c) may vary within the range of about 9: 1 to 1: 9. A preferred range is from about 4: 1 to 1: 4.
It is. Examples of molar ratios of reactants (a), (b) and (c) that are considered useful in this monomer mixture include 1: 0.
6: 0.4, 1: 0.8: 0.2, 1: 0.9: 0.1, 1: 0.2: 0.8,
1: 0.1: 0.9 and 1: 0.3: 0.4 are included.

The polymerization of these three reactants is carried out in the presence of a small amount of a catalyst at a temperature of about 25 ° C. to about 150 ° C., preferably at a temperature of about 25 ° C. to about 100 ° C., in a solvent or diluent. This is accomplished by mixing and heating these reactants, with or without agents. Since the polymerization is exothermic, to maintain the reaction mixture at the desired temperature,
May require cooling. To control the rate of the polymerization reaction, it is often convenient to add one of these reactants to a mixture of the other two reactants.
Generally, the vinyl ester and the alkyl vinyl ether are mixed and slowly added to the fumarate-catalyst mixture.

This polymerization is carried out in the presence of a small amount of a catalyst (for example, an organic peroxide or azobisisobutyronitrile). Organic peroxides such as benzoyl peroxide and chlorobenzoyl peroxide are particularly useful. Generally, about 0.01 to about 1.5% of the catalyst is used.

The reaction time may vary from about 1 to about depending on the temperature, the reactivity of these monomers and other reaction conditions.
It changes in 30 hours.

The exact nature of the terpolymer is not completely understood. However, it has been found that the properties of this polymer depend on the choice of monomer ratio. Thus, while the composition of the terpolymer is controlled by such a choice, its exact chemical composition remains unknown.

The terpolymer is characterized by the specific viscosity at 30 ° C. of 5 grams of terpolymer and 100 ml of benzene. It is well known that the specific viscosity of a polymer solution is an indicator of the molecular weight of the polymer. This specific viscosity is defined by the following equation:

[0237]

(Equation 2) A solution containing 5 grams of the terpolymer of the invention per 100 ml of benzene is characterized by a specific viscosity (30 ° C.) of 0.090 to 0.800.

The following examples illustrate the preparation of the terpolymers of the present invention.

Example (E-16) 2340 parts (12 mol) of a commercial mixture of a fatty alcohol consisting of 2% decyl alcohol, 65% dodecyl alcohol, 26% tetradecyl alcohol and 7% hexadecyl alcohol, and paratoluenesulfonic acid 12.5 parts of a mixture are prepared and to this mixture 696 parts (6 mol) of fumaric acid are added. This esterification, while removing the water formed,
This is achieved by heating the mixture at reflux for 6 hours. To this mixture, add calcium hydroxide (30
Parts) and 50 parts of a filter aid, which are heated to 110 ° C. over 1 hour and filtered. The filtrate is heated to 145 ° C./30 mm. To remove volatile components. This residue is the desired dialkyl fumarate having a saponification number of 231 (theoretical, 238).

A mixture of 25 parts (0.3 mol) of vinyl acetate and 14 parts (0.2 mol) of ethyl vinyl ether was added dropwise to 254 parts (0.5 mol) of the mixture of dialkyl fumarate prepared above.
Warm to 37 ° C and add azobisisobutyronitrile 1.5
Add parts. The mixture was then heated to 85 ° C,
Then, it is maintained at a temperature of 60 ° C to 70 ° C for 10 hours. This is 135
The volatile constituents are removed by heating at 40 ° C./40 mm. This residue is the desired terpolymer having a specific viscosity of 0.295 in benzene solution.

Example (E-17 ) A mixture of 34.4 parts (0.4 mol) of vinyl acetate and 7.2 parts (0.10 mol) of ethyl vinyl ether was heated at 41 ° C. in a nitrogen atmosphere.
At a temperature of ~ 44 ° C, it is added dropwise to 237 parts (0.5 mol) of a dialkyl fumarate (saponification value of 231) prepared as in Example (E-16). Then, after addition of 1.4 parts of azobisisobutyronitrile, some polymerization takes place after about 5 hours. After heating for a further 8 hours, 2 parts of chlorobenzyl peroxide are added and the reaction mixture is maintained at 50-60 ° C. for 1 hour. The mixture is then heated to 80 ° C. at 20 mm Hg to remove any volatiles, a filter aid is added and the mixture is filtered at a temperature of 130 ° C. This filtrate is the desired terpolymer having a specific viscosity of 0.524 in a benzene solution.

Example (E-18) A mixture of 17.2 parts (0.2 mol) of vinyl acetate and 21.6 parts (0.3 mol) of ethyl vinyl ether was prepared in Example (E-16) at a temperature of 28 ° C. for 5 minutes. Dialkyl fumarate
(Saponification value of 218) 237 parts (0.5 mol). Then
1.4 parts of azobisisobutyronitrile are added and the mixture is heated to 55-60 ° C. This mixture is brought to 55 ° C to 60 ° C.
Maintain at a temperature of ° C. for 3 hours and filter with a filter aid. This filtrate is the desired terpolymer having a specific viscosity of 0.358 in benzene solution.

Example (E-19) 8.6 parts (0.1 mol) of vinyl acetate and ethyl vinyl ether
A mixture of 28.8 parts (0.40 mol) of dialkyl fumarate 23 prepared in Example (E-17) at a temperature of 40 ° C. in a nitrogen atmosphere.
7 parts (0.50 mol) are added dropwise. The reaction is slightly exothermic and the mixture is maintained at a temperature between 50 ° C and 60 ° C for 15 hours. The mixture is then heated at 160 ° C./15 mm. To remove any volatiles. A filter aid is added and the mixture is filtered at a temperature of 82 ° C. This filtrate is the desired terpolymer having a specific viscosity of 0.183 in a benzene solution.

Example (E-20) Vinyl acetate (40 parts, 0.46 mol) was added at a temperature of 40 ° C. to 42 ° C.
Add to 380 parts (0.75 mol) of dialkyl fumarate (236 saponification value) prepared according to the method of Example (E-16), followed by
22 parts (0.31 mol) of ethyl vinyl ether and 4.4 parts of benzoyl peroxide are added. The mixture is brought to 66 ° C for 45 minutes.
And maintain at that temperature for 6.5 hours. Then mineral oil (221 parts) is added, the solution is reheated to 66 ° C and filtered. This filtrate is the desired terpolymer solution (33.3% oil) with a specific viscosity of 0.390 in benzene solution.

Example (E-21) A commercial mixture of 1 mol of fumaric acid and a fatty alcohol (this is 2.5% decyl alcohol, 95.0% dodecyl alcohol)
215 parts (0.5 mol) of dialkyl fumarate, 34.3 parts (0.3 mol) of vinyl butyrate, 14.4 parts (0.2 mol) of ethyl vinyl ether and a catalyst prepared by reacting with 2 mol of The procedure of Example (E-16) is repeated using 1.5 parts of benzoyl peroxide as

The biodegradable fortified grease is prepared by mixing together components (A) and (B). Ingredient (C)
Is formed in situ by the reaction of components (C1) and (C2). After forming component (C), additional solutions of components (A) and (B) may be added.

In obtaining the compositions of the present invention, two different methods are envisioned. In the first method, the grease is prepared including the following steps (a), (b), (c) and (d): (a) (A) base oil and (B) performance Additive or (A) base oil, (B) performance additive, (D) viscosity improver and / or (E) pour point depressant with (C1) metal-based material and (C2) carboxylic acid or ester thereof A process of producing a solution, wherein:
The equivalent ratio of (C1) :( C2) is about 1: 0.70 to 1.10, where the base oil (A) and the sum of the metal base material (C1) and the carboxylic acid or its ester (C2) Weight ratio is 50: 50 ~
95: 5, whereby a mixture is provided, wherein (b) heating the mixture to a temperature of from 82C to about 105C;
(C) forming a thickening agent; (c) heating the mixture to about 145 ° C. in the case of an alkaline earth metal.
Final temperature, or about 200 ° C for alkali metals
And d) cooling the mixture to form grease.

The second method of the present invention comprises the following steps: (a) (A) base oil and (B) performance additive or (A) base oil, (B) performance additive, (D) A) preparing a solution of a viscosity improver and / or (E) a pour point depressant and (C1) a metal-based material and (C2) a carboxylic acid or an ester thereof, wherein
The equivalent ratio of (C1) :( C2) is about 1: 0.70-1.10, where the base oil (A) and the sum of the metal base material (C1) and the carboxylic acid or its ester (C2) Weight ratio is 50: 50 ~
95: 5, thereby providing a first mixture;
(B) heating the first mixture to a temperature of about 82 ° C. to about 105 ° C. to form (C) a thickener, thereby forming a heated first mixture; (c) ) Heating the heated first mixture to a final temperature of about 145 ° C. in the case of an alkaline earth metal, or about 200 ° C. in the case of an alkali metal; At 110-145 ° C for metals or 170-200 ° C for alkali metals, base oil
(A) the next portion of the base oil, or so that the total weight ratio of (A) and the total of the metal base material (C1) and the carboxylic acid or its ester (C2) is 50:50 to 95: 5, or (A) base oil and
A solution of (B) a performance additive, or a solution of (A) a base oil, (B) a performance additive, (D) a viscosity improver, and / or (E) a pour point depressant, is added to the second mixture. Providing; and (e) cooling the second mixture to form a grease.

In the above method, the total weight% of the performance additive (B) in the grease is 0.5 to 10, preferably 1 to 6, most preferably 1.25 to 3. The total weight% of the viscosity modifier (D) in the grease is 0.5 to 7.5, preferably 0.75
-5, most preferably 1-3. The total weight percentage of pour point depressant (E) in the grease is 0.5-7.5, preferably 0.75-5, most preferably 1-3.

In the above method, (A), (B), (C1), (C2),
(D) and (E) are the same as defined above.

Example 1 A blend of Sunyl 80 oil and additives is prepared as follows: 24,244 parts Sunyl 80 oil, Gl available from BASF
issoviscal PGE (762 parts), nonylated diphenylamine 19
0.5 parts, 190.5 parts of 2,6-di-t-butylphenol and 12.7 parts of tolyltriazole. Heat this oil to 70 ° C,
Add these additives and stir until a homogeneous solution is obtained.

In a Hobart mixer, mix the above compounded oil 1,270
Parts, and 240 parts of 12-hydroxystearic acid (0.8 equivalent)
Is added. Heat the contents, stir, and
At 77 ° C., 32.8 parts (0.88 equivalents) of calcium hydroxide are added. Slowly raise this temperature to 140 ° C and at this temperature
Hold for 0.5 hour. Turn off the heat and add 457.2 parts of this blended oil. A grease forms at about 60 ° C. and the contents are ground.

Example 2 A blend of rapeseed oil and additives is prepared as follows: 25,006 parts of rapeseed oil, nonylated diphenylamine
190.5 parts, 190.5 parts of 2,6-di-t-butylphenol and 12.7 parts of tolyltriazole. Heat the oil to 70 ° C., add these additives and stir until a homogeneous solution is obtained.

Sunyl compounded according to the method of Example 1
Grease is prepared using compounded rapeseed oil instead of 80 oil.

Example 3 To a Hobart mixer are added 1,400 parts of the rapeseed oil of Example 2 and 195 parts (0.65 equivalents) of 12-hydroxystearic acid. The contents are heated to 77 ° C. and a mixture of 35 parts (0.83 equivalent) of lithium hydroxide monohydrate and 80 parts of water is slowly added. This temperature is raised to 103 ° C. while removing water. The contents are slowly heated to 195 ° C. and held at this temperature for 10 minutes. Turn off the heat and add 370 parts of compounded rapeseed oil. Upon cooling, grease is formed and the contents are ground.

Example 4 In a Hobart mixer, blend the Sunyl 80 oil of Example 1 with 1,587.4
And 258 parts (0.86 equivalents) of 12-hydroxystearic acid are added. Heat the contents to 77 ° C. and add a mixture of 46.2 parts (1.1 equivalents) of lithium hydroxide monohydrate and 80 parts of water,
Add slowly. While removing water, raise this temperature to 103
Increase to ° C. The contents are slowly heated to 175 ° C. and held at this temperature for 30 minutes. Turn off the heat and add 108 parts of formulated Sunyl 80 oil. Upon cooling, grease is formed and the contents are ground.

Example 5 An oil formulation is prepared to give a Sunyl 80 oil formulation in a manner similar to the method and proportions of the rapeseed oil formulation of Example 2, except that the rapeseed oil is replaced with Sunyl 80 oil. this
The procedure of Example 1 is repeated using a Sunyl 80 oil formulation to prepare a grease composition.

Example 6 The procedure of Example 5 is essentially followed, except that the water is omitted.

The grease compositions according to the invention are evaluated in the following tests: unmixed penetration, P ₀ ; admixed penetration, P ₆₀ and P _10K ; dropping point; welding point and wear. Some of the greases prepared above have the following properties as shown in Table 1.

[0260]

[Table 1]

[0261]

According to the present invention, it is possible to provide a grease composition produced from a vegetable oil-containing antioxidant and a viscosity improver, and a method for preparing the same. The lubricating grease of the present invention is biodegradable and environmentally friendly.

──────────────────────────────────────────────────続 き Continued on the front page (51) Int.Cl. ⁶ Identification code Agency reference number FI Technical indication location C10M 133: 44 133: 12 117: 06 117: 02) C10N 10:02 10:04 30:00 50 : 10 (71) Applicant 591131338 29400 Lakeland Boulevard, Wicklife, Ohio 44092, United States of America (72) Inventor Kasuturi Lal India Gargaon 120001, sector 17 883

Claims (22)

[Claims] (1) It comprises the following (A), (B) and (C):
Eco-friendly lubricating grease: (A) a base oil, wherein the base oil is a natural oil or a synthetic triglyceride of the formula: Wherein R ¹ , R ² and R ³ are aliphatic groups containing from about 7 to about 23 carbon atoms; (B) containing the following (1), (2) or (3) Yes, at least one
Kinds of performance additives: (1) Alkyl phenols of the following formula: Wherein R ⁴ is an alkyl group containing from 1 to about 24 carbon atoms, and a is an integer from 1 to 5; (2) a benzotriazole of the following formula: ] Wherein R ⁵ is hydrogen or an alkyl group having from 1 to about 24 carbon atoms; or (3) an aromatic amine of the following formula: Here, R ⁶ is And R ⁷ and R ⁸ are independently hydrogen, or an alkyl group containing from 1 to about 24 carbon atoms; and (C) a thickener, wherein The thickener (C) is a reaction product of (C1) a metal-based material and (C2) a carboxylic acid or an ester thereof, wherein the metal-based material (C1) is
A metal oxide, metal hydroxide, metal carbonate or metal bicarbonate, wherein the metal is an alkali metal or alkaline earth metal, wherein the carboxylic acid or ester thereof (C2) Has the formula R ¹⁸ (COOR ¹⁹ ) _n , wherein R ¹⁸ is an aliphatic group containing from 4 to about 29 carbon atoms, and R ¹⁹ is hydrogen or 1 to 4 And n is an integer from 1 to 4, where the equivalent ratio of (C1) :( C2) is 1: 0.70 to 1.
It is 10. 2. The lubricating grease of claim 1, wherein said alkyl phenol has the formula: Here, R ⁴ is t-butyl. 3. The lubricating grease according to claim 1, wherein in (B) (2), R ⁵ is a methyl group. (4) In (B) (3), R ⁶ is The lubricating grease according to claim 1, wherein R ^{7 and} R ⁸ are nonyl groups. 5. The method according to claim 1, wherein the alkali metal of (C1) is lithium,
The lubricating grease of claim 1, comprising sodium or potassium, and wherein said alkaline earth metal of (C1) comprises magnesium, calcium or barium. 6. The lubricating grease according to claim 1, wherein (C1) is lithium hydroxide or calcium hydroxide. 7. A monohydroxy compound, wherein R ¹⁹ is hydrogen and said carboxylic acid comprises 6-hydroxystearic acid, 12-hydroxystearic acid, 14-hydroxystearic acid, 16-hydroxystearic acid or ricinoleic acid. The lubricating grease of claim 1, wherein the grease is a monocarboxylic acid or a dihydroxymonocarboxylic acid, including 9,10-dihydroxystearic acid. 8. The natural oil is a sunflower oil, a safflower oil, a corn oil, a soybean oil, a rapeseed oil, a coconut oil, a resclara oil, a castor oil, a canola oil or a peanut oil.
The lubricating grease according to claim 1. 9. The lubricating grease of claim 1, wherein the synthetic triglyceride is an ester of at least one straight chain fatty acid and glycerol, wherein the fatty acid contains from 8 to 22 carbon atoms. 10. The natural oil is a genetically modified vegetable oil, wherein R ¹ , R ² and R ³ are aliphatic groups having at least 60% monounsaturated properties, wherein the monounsaturated properties are Wherein the ratio of the oleic acid moiety to the linoleic acid moiety is from 2 to 90, wherein the genetically modified vegetable oil is a genetically modified sunflower oil, a genetically modified Corn oil, genetically modified soybean oil,
The lubricating grease according to claim 1, which is a genetically modified rapeseed oil, a genetically modified canola oil, a genetically modified safflower oil or a genetically modified peanut oil. 11. The lubricating grease according to claim 1, further comprising the following (D) or (E): (D) a hydrogenated block copolymer containing a normal block copolymer or a random block copolymer. A viscosity improver containing a coalesce, wherein the normal block copolymer is made from a vinyl-substituted aromatic compound and an aliphatic conjugated diene, and the normal block copolymer is at least one of the vinyl-substituted aromatic compounds. And from 2 to about 5 polymer blocks having at least one polymer block and at least one polymer block of the aliphatic conjugated diene, wherein the random block copolymer comprises a vinyl-substituted aromatic monomer and Manufactured from an aliphatic conjugated diene monomer, the total amount of the vinyl-substituted aromatic block in the block copolymer is about
The total amount of the diene blocks in the block copolymer ranges from about 30% to about 80% by weight, and the normal block copolymer and the random The number average molecular weight of the block copolymer is about 5,000
A viscosity modifier ranging from 0 to about 1,000,000; or (E) a pour point depressant, or a mixture thereof. 12. The normal block copolymer has a total of two or three polymer blocks, and the number average molecular weight of the normal block copolymer and the random block copolymer is about 30,000 to About 200,000, and in the block copolymer, the total amount of the conjugated diene is
About 40% to about 60% by weight, wherein the total amount of the vinyl-substituted aromatic compound is about 40% to about 60% by weight; the conjugated diene is isoprene or butadiene; The lubricating grease of claim 11, wherein the compound is styrene and the hydrogenated normal block copolymer and random block copolymer contain no more than 0.5% residual olefinic unsaturation. 13. The pour point depressant (E) is a mixed ester characterized by the low temperature improving properties of an ester of a carboxy-containing interpolymer, said interpolymer having a reduced specific viscosity of about 0.05 to about 2. And one or more monomers derived from at least two monomers, wherein one of the monomers is a low molecular weight aliphatic olefin, styrene or substituted styrene, wherein the substituent is from 1 to about 18 carbon atoms. And the other of the monomers is an α, β-unsaturated aliphatic acid, anhydride or ester thereof, wherein the mixed ester has substantially no titratable acidity. And the following (a), (b) and (c) derived from the carboxy group of the mixed ester:
The lubricating grease of claim 11, wherein the pendant polar group of at least 8 aliphatic carbon atoms in the ester group is characterized by being present in the polymer structure. A carboxylic acid ester group of a molecular weight, if necessary, (b) a relatively low molecular weight carboxylic acid ester group having 7 or less aliphatic carbon atoms in the ester group,
Here, when (b) is present, (a) of the pour point depressant:
The molar ratio of (b) is (1-20): 1, a relatively low molecular weight carboxylic ester group, and, if necessary, (c) one primary amino group or secondary amino group. A carbonyl-amino group derived from an amino compound having a group, wherein when (b) and (c) are present, the moles of (a) :( b) :( c) of the pour point depressant The ratio is (50-100) :( 5-5
0): carbonyl-amino group, which is (0.1 to 15). 14. The pour point depressant wherein the molar ratio of (a) :( b) is (1-10): 1 or the pour point depressant is
The molar ratio of (a) :( b) :( c) is (70-85) :( 15-30) :( 1
The lubricating grease according to claim 13, which is 5). 15. The interpolymer of claim 1, wherein the interpolymer is a styrene-maleic anhydride interpolymer having a reduced specific viscosity of about 0.1 to about 1, wherein the relatively high molecular weight carboxylic acid ester groups (a) have from 8 to 24 carboxylic acid ester groups. Aliphatic carbon atoms, the relatively low molecular weight carboxylic acid ester group (b)
Has 3 to 5 carbon atoms, and the carbonyl-amino group (c) is derived from a primary aminoalkyl-substituted tertiary amine. 16. The lubricating grease of claim 13, wherein said carboxy-containing interpolymer is a terpolymer of 1 mole proportion of styrene, 1 mole proportion of maleic anhydride, and less than about 0.3 mole proportion of vinyl monomer. . 17. The lubricating grease of claim 11, wherein said pour point depressant (E) is an acrylate polymer of the formula: Here, R ⁹ is hydrogen or a lower alkyl group containing 1 to about 4 carbon atoms, R ¹⁰ is an alkyl group containing about 1 to about 24 carbon atoms, a cycloalkyl group or A mixture of aromatic groups, and x is an integer that provides the acrylate polymer with a weight average molecular weight (Mw) of about 5,000 to about 1,000,000. 18. The lubricating grease of claim 11, wherein said pour point depressant (E) is a mixture of compounds having the following general structure: Here, Ar, Ar ′ and Ar ″ are each independently an aromatic moiety containing 1 to 3 aromatic rings, and the mixture may be such that the moiety is present without a substituent. , one substituent, alkylene include two compounds present with substituents and 3 substituents, R ¹¹ and R ^12, which independently contains from about 1 to 100 carbon atoms , N is 0-1000, and n ′ is 0 or 1, and X is a hydrocarbylene group containing from 1 to 24 carbon atoms, wherein the compound is It has a molecular weight ranging from 300 to about 300,000. 19. The pour point depressant (E) may comprise an acrylate monomer of the following formula and a nitrogen-containing monomer in a ratio of 0.001 to 1.0 mole of the nitrogen-containing monomer to each mole of the acrylate monomer. Is a nitrogen-containing polymer prepared by polymerization in the above, the nitrogen-containing monomer is 4-vinylpyridine, 2-vinylpyridine, 2-N-morpholinoethyl methacrylate, N, N-dimethylaminoethyl methacrylate and methacryl The lubricating grease of claim 11, wherein the grease is selected from the group consisting of N, N-dimethylaminopropyl acid. Wherein R ¹³ is hydrogen or an alkyl group containing from 1 to about 8 carbon atoms, and R ¹⁴ is from 1 to about 3
It is an alkyl, cycloalkyl or aromatic group containing 0 carbon atoms. 20. The pour point depressant (E) is a terpolymer, and the terpolymer is a solution of 5 grams of the terpolymer per 100 ml of benzene at 30 ° C. Having a specific viscosity of 0.090 to 0.800, measured at 25 ° C to 150 ° C.
At a temperature of ° C., the following (a) 1 mol, the following (b) and
The lubricating grease according to claim 11, which is prepared by polymerizing 0.5 to 1 mol of the mixture of (c): (a) fumaric acid ester of the following formula: Wherein R ¹⁵ is an alkyl group containing 10 to 18 carbon atoms; (b) a vinyl ester of the following formula: Wherein R ¹⁶ is an alkyl group containing 2 to 10 carbon atoms; (c) a vinyl ether of the following formula: Here, R ¹⁷ is an alkyl group containing 1 to 10 carbon atoms, and the molar ratio of (b) to (c) in the mixture is 9:
It is in the range of 1-1: 9. 21. A method for preparing an environmentally friendly grease, comprising the steps of: (a) preparing a solution of the following (A) and (B): (A) a base oil, wherein: The base oil is a natural oil or a synthetic triglyceride of the formula: Wherein R ¹ , R ² and R ³ are aliphatic groups containing from about 7 to about 23 carbon atoms; (B) containing the following (1), (2) or (3) Yes, at least one
Kinds of performance additives: (1) alkylphenol of the following formula: Wherein R ⁴ is an alkyl group containing from 1 to about 24 carbon atoms, and a is an integer from 1 to 5; (2) benzotriazole of the following formula: ] Wherein R ⁵ is hydrogen or an alkyl group having from 1 to about 24 carbon atoms; or (3) an aromatic amine of the formula: Here, R ⁶ is And R ⁷ and R ⁸ are independently hydrogen or an alkyl group containing from 1 to about 24 carbon atoms; or (A), (B) and (D) (A) a base oil; (B) a performance additive; and (D) a viscosity improver, wherein the viscosity improver is a normal block copolymer or a random block copolymer. A hydrogenated block copolymer containing a copolymer, wherein the normal block copolymer is produced from a vinyl-substituted aromatic compound and an aliphatic conjugated diene, and the normal block copolymer is at least one of the vinyl-substituted aromatic compound. One polymer block and at least one of the aliphatic conjugated dienes
Having from 2 to about 5 polymer blocks, wherein the random block copolymer is made from a vinyl-substituted aromatic monomer and an aliphatic conjugated diene monomer; The total amount of the vinyl substituted aromatic blocks in the block copolymer ranges from about 20% to about 70% by weight, and the total amount of the diene blocks in the block copolymer ranges from about 30% to about 80% by weight. The number average molecular weight of the normal block copolymer and the random block copolymer ranges from about 5,000 to about 1,000,000;
Or a process for producing a solution of the following (A), (B) and (E): (A) a base oil; (B) a performance additive; and (E) a pour point depressant, said pour point depressant. Agent (E) comprises a mixed ester characterized by the low temperature improving properties of the ester of the carboxy-containing interpolymer, the interpolymer having a reduced specific viscosity of about 0.05 to about 2 and at least two monomers Wherein one of the monomers is a low molecular weight aliphatic olefin, styrene or substituted styrene, wherein the substituent is a hydrocarbyl group containing from 1 to about 18 carbon atoms; And the other of the monomers is an α, β-unsaturated aliphatic acid, anhydride or ester thereof, the mixed ester has substantially no titratable acidity, and the carboxy group of the mixed ester The following (a), (b) And (c) the pendant polar group is characterized by being present in the polymer structure: (a) a relatively high molecular weight carboxylic acid having at least 8 aliphatic carbon atoms in the ester group; An acid ester group, optionally, (b) a relatively low molecular weight carboxylic ester group having 7 or less aliphatic carbon atoms in the ester group,
Here, when (b) is present, (a) of the pour point depressant:
The molar ratio of (b) is (1-20): 1, a relatively low molecular weight carboxylic ester group, and, if necessary, (c) one primary amino group or secondary amino group. A carbonyl-amino group derived from an amino compound having a group, wherein when (b) and (c) are present, the moles of (a) :( b) :( c) of the pour point depressant The ratio is (50-100) :( 5-5
0): a carbonyl-amino group which is (0.1-15); or the pour point depressant comprises an acrylate polymer of the formula: Here, R ⁹ is hydrogen or a lower alkyl group containing 1 to about 4 carbon atoms, R ¹⁰ is an alkyl group containing about 1 to about 24 carbon atoms, a cycloalkyl group or A mixture of aromatic groups, and x is an integer that provides the acrylate polymer with a weight average molecular weight (Mw) of about 5,000 to about 1,000,000; or the pour point depressant is
It contains a mixture of compounds having the following general structural formula: Here, Ar, Ar ′ and Ar ″ are each independently an aromatic moiety containing 1 to 3 aromatic rings, and the mixture may be such that the moiety is present without a substituent. , one substituent, alkylene include two compounds present with substituents and 3 substituents, R ¹¹ and R ^12, which independently contains from about 1 to 100 carbon atoms , N is 0-1000, and n ′ is 0 or 1, and X is a hydrocarbylene group containing from 1 to 24 carbon atoms; or the pour point depressant is An acrylate monomer and a nitrogen-containing monomer represented by the following formula, for each mole of the acrylate monomer, the nitrogen-containing monomer 0.001 to 1.0
Contains a nitrogen-containing polymer prepared by polymerizing in molar proportions: Wherein R ¹³ is hydrogen or an alkyl group containing from 1 to about 8 carbon atoms, and R ¹⁴ is from 1 to about 3
An alkyl group, a cycloalkyl group or an aromatic group containing 0 carbon atoms; or the pour point depressant is a terpolymer, and the terpolymer is at 30 ° C., benzene
Has a specific viscosity of 0.090-0.800, measured in a solution of 5 grams of the terpolymer per 100 milliliters, and
By polymerizing the following (a) 1 mol and the following mixture of (b) and (c) 0.5 to 1 mol at a temperature of ~ 150 ° C,
Prepared: (a) Fumaric ester of the formula: Wherein R ¹⁵ is an alkyl group containing 10 to 18 carbon atoms; (b) a vinyl ester of the following formula: Wherein R ¹⁶ is an alkyl group containing 2 to 10 carbon atoms; (c) a vinyl ether of the following formula: Here, R ¹⁷ is an alkyl group containing 1 to 10 carbon atoms, and the molar ratio of (b) to (c) in the mixture is 9:
1-1: 9; or the following (A), (B), (D)
And (E) to produce a solution: (A) a base oil; (B) a performance additive; (D) a viscosity improver; and (E) a pour point depressant; and (C1) a metal-based material and (C)
2) adding a carboxylic acid or an ester thereof, thereby providing a mixture: wherein the metal-based material
(C1) comprises a metal oxide, metal hydroxide, metal carbonate or metal bicarbonate, wherein the metal is an alkali metal or alkaline earth metal, wherein the carboxylic acid or esters thereof (C2) has the formula _{^{R 18 (COOR 1 9) n}} , wherein, R ¹⁸ is an aliphatic group containing from 4 to about 29 carbon atoms, R ¹⁹ is hydrogen Or an aliphatic group containing 1 to 4 carbon atoms, and n is 1 to
4, where the equivalent ratio of (C1) :( C2) is 1:
0.70 to 1.10, wherein the base oil (A), the metal base material (C1) and the carboxylic acid or its ester (C2)
Weight ratio to the sum of is 50:50 to 95: 5; and (b) heating the mixture to a temperature of about 82 ° C to about 105 ° C;
(C) forming a thickening agent; (c) heating the mixture to about 145 ° C. in the case of an alkaline earth metal.
Final temperature, or about 200 ° C for alkali metals
And (d) cooling the mixture to form a grease, wherein the performance additive (B) is present at 0.5-10% by weight and the viscosity The modifier (D) is present at 0.5-7.5% by weight and the pour point depressant (E) is present at 0.5-7.5% by weight. 22. A method for preparing an environmentally friendly grease, comprising: (a) producing a solution of the following (A) and (B): (A) a base oil, wherein: The base oil is a natural oil or a synthetic triglyceride of the formula: Wherein R ¹ , R ² and R ³ are aliphatic groups containing from about 7 to about 23 carbon atoms; (B) containing the following (1), (2) or (3) Yes, at least one
Kinds of performance additives: (1) alkylphenol of the following formula: Wherein R ⁴ is an alkyl group containing from 1 to about 24 carbon atoms, and a is an integer from 1 to 5; (2) a benzotriazole of the following formula: ] Wherein R ⁵ is hydrogen or an alkyl group having from 1 to about 24 carbon atoms; or (3) an aromatic amine of the following formula: Here, R ⁶ is And R ⁷ and R ⁸ are independently hydrogen or an alkyl group containing from 1 to about 24 carbon atoms; or (A), (B) and (D) (A) a base oil; (B) a performance additive; and (D) a viscosity improver, wherein the viscosity improver comprises a normal block copolymer or a random block copolymer. A hydrogenated block copolymer, wherein the normal block copolymer is made from a vinyl-substituted aromatic compound and an aliphatic conjugated diene, the normal block copolymer comprising at least one of the vinyl-substituted aromatic compound A polymer block and at least one polymer block of the aliphatic conjugated diene having from 2 to about 5 polymer blocks, wherein the random block copolymer comprises a vinyl-substituted aromatic monomer and an aliphatic Conjugated dienmo And the total amount of the vinyl-substituted aromatic blocks in the block copolymer ranges from about 20% to about 70% by weight, and the total amount of the diene blocks in the block copolymer is: About 30
% To about 80% by weight, and the number average molecular weight of the normal block copolymer and the random block copolymer ranges from about 5,000 to about 1,000,000; or the following (A), (B) ) And (E): (A) a base oil; (B) a performance additive; and (E) a pour point depressant, wherein the pour point depressant (E) comprises A mixed ester characterized by the low temperature improving properties of the ester of the polymer, wherein the interpolymer has a reduced specific viscosity of about 0.05 to about 2 and is derived from at least two monomers, one of the monomers being A low molecular weight aliphatic olefin, styrene or substituted styrene, wherein the substituent is a hydrocarbyl group containing from 1 to about 18 carbon atoms and the other of the monomers is α, β-unsaturated aliphatic acids, An anhydride or an ester, wherein the mixed ester has substantially no titratable acidity and is derived from the carboxy group of the mixed ester and comprises the following (a), (b) and (c): A pendant polar group is characterized by the presence in the polymer structure: (a) a relatively high molecular weight carboxylic ester group having at least 8 aliphatic carbon atoms in the ester group; (B) a relatively low molecular weight carboxylic ester group having 7 or less aliphatic carbon atoms in the ester group,
Here, when (b) is present, (a) of the pour point depressant:
The molar ratio of (b) is (1-20): 1, a relatively low molecular weight carboxylic ester group, and, if necessary, (c) one primary amino group or secondary amino group. A carbonyl-amino group derived from an amino compound having a group, wherein when (b) and (c) are present, the moles of (a) :( b) :( c) of the pour point depressant The ratio is (50-100) :( 5-5
0): a carbonyl-amino group which is (0.1-15); or the pour point depressant comprises an acrylate polymer of the formula: Here, R ⁹ is hydrogen or a lower alkyl group containing 1 to about 4 carbon atoms, R ¹⁰ is an alkyl group containing about 1 to about 24 carbon atoms, a cycloalkyl group or A mixture of aromatic groups, and x is an integer that provides the acrylate polymer with a weight average molecular weight (Mw) of about 5,000 to about 1,000,000; or the pour point depressant is
It contains a mixture of compounds having the following general structural formula: Here, Ar, Ar ′ and Ar ″ are each independently an aromatic moiety containing 1 to 3 aromatic rings, and the mixture may be such that the moiety is present without a substituent. , one substituent, alkylene include two compounds present with substituents and 3 substituents, R ¹¹ and R ^12, which independently contains from about 1 to 100 carbon atoms , N is 0-1000, and n ′ is 0 or 1, and X is a hydrocarbylene group containing from 1 to 24 carbon atoms; or the pour point depressant is An acrylate monomer and a nitrogen-containing monomer represented by the following formula, for each mole of the acrylate monomer, the nitrogen-containing monomer 0.001 to 1.0
Contains a nitrogen-containing polymer prepared by polymerizing in molar proportions: Wherein R ¹³ is hydrogen or an alkyl group containing from 1 to about 8 carbon atoms, and R ¹⁴ is from 1 to about 3
An alkyl group, a cycloalkyl group or an aromatic group containing 0 carbon atoms; or the pour point depressant is a terpolymer, and the terpolymer is at 30 ° C., benzene
Has a specific viscosity of 0.090-0.800, measured in a solution of 5 grams of the terpolymer per 100 milliliters, and
By polymerizing the following (a) 1 mol and the following mixture of (b) and (c) 0.5 to 1 mol at a temperature of ~ 150 ° C,
Prepared: (a) Fumaric ester of the formula: Wherein R ¹⁵ is an alkyl group containing 10 to 18 carbon atoms; (b) a vinyl ester of the following formula: Wherein R ¹⁶ is an alkyl group containing 2 to 10 carbon atoms; (c) a vinyl ether of the following formula: Here, R ¹⁷ is an alkyl group containing 1 to 10 carbon atoms, and the molar ratio of (b) to (c) in the mixture is 9:
1-1: 9; or the following (A), (B), (D)
(A) base oil; (B) performance additive; (D) viscosity improver; and (E) pour point depressant; and (C1) metal-based material and (C)
2) adding a carboxylic acid or an ester thereof, thereby providing a first mixture: wherein the metal-based material (C1) is a metal oxide, a metal hydroxide, a metal carbonate or a metal oxide; A carbonate, wherein the metal is an alkali metal or alkaline earth metal, wherein the carboxylic acid or its ester (C2) has the formula R ¹⁸ (COOR ¹⁹ ) _n , Wherein R ¹⁸ is an aliphatic group containing from 4 to about 29 carbon atoms, R ¹⁹ is hydrogen, or an aliphatic group containing from 1 to 4 carbon atoms, and n Is 1
Where the equivalent ratio of (C1) :( C2) is
1: 0.70 to 1.10, wherein the base oil (A), the metal base material (C1) and the carboxylic acid or its ester
The weight ratio of (C2) to the sum is from 50:50 to 90:10; and (b) heating the first mixture to a temperature of about 82 ° C to about 105 ° C, Forming an agent, thereby forming a heated first mixture; (c) subjecting the heated first mixture to a final temperature of about 145 ° C. in the case of an alkaline earth metal, or in the case of an alkali metal Heating to a final temperature of about 200 ° C .; (d) at 110-145 ° C. for alkaline earth metals, or 170-200 ° C. for alkali metals,
The next part of (A), or ( Adding a solution of A) and (B), or a solution of (A), (B), (D) and / or (E) to provide a second mixture; and (e) the second mixture Cooling to form a grease: wherein the performance additive (B) is present at 0.5-10% by weight, the viscosity modifier (D) is present at 0.5-7.5% by weight, And the pour point depressant (E) is present at 0.5-7.5% by weight.